U.S. patent application number 13/424856 was filed with the patent office on 2012-07-12 for substrate and method for the formation of continuous magnesium diboride and doped magnesium diboride wires.
This patent application is currently assigned to SPECIALTY MATERIALS, INC.. Invention is credited to Janet Suplinskas, Raymond J. Suplinskas.
Application Number | 20120178631 13/424856 |
Document ID | / |
Family ID | 32393511 |
Filed Date | 2012-07-12 |
United States Patent
Application |
20120178631 |
Kind Code |
A1 |
Suplinskas; Raymond J. ; et
al. |
July 12, 2012 |
SUBSTRATE AND METHOD FOR THE FORMATION OF CONTINUOUS MAGNESIUM
DIBORIDE AND DOPED MAGNESIUM DIBORIDE WIRES
Abstract
A chemically doped boron coating is applied by chemical vapor
deposition to a silicon carbide fiber and the coated fiber then is
exposed to magnesium vapor to convert the doped boron to doped
magnesium diboride and a resultant superconductor.
Inventors: |
Suplinskas; Raymond J.;
(Haverhill, MA) ; Suplinskas; Janet; (Haverhill,
MA) |
Assignee: |
SPECIALTY MATERIALS, INC.
Lowell
MA
|
Family ID: |
32393511 |
Appl. No.: |
13/424856 |
Filed: |
March 20, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11937092 |
Nov 8, 2007 |
8163344 |
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13424856 |
|
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10989803 |
Nov 17, 2004 |
7294606 |
|
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11937092 |
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PCT/US03/20628 |
Jul 1, 2003 |
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10989803 |
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60429137 |
Nov 26, 2002 |
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Current U.S.
Class: |
505/500 ;
252/500; 252/520.22; 505/300 |
Current CPC
Class: |
C04B 35/62878 20130101;
Y10T 428/2991 20150115; C04B 35/62873 20130101; C04B 35/62857
20130101; C23C 16/28 20130101; C04B 2235/3813 20130101; C04B
2235/48 20130101; C04B 2235/94 20130101; C23C 16/56 20130101; C04B
2235/3808 20130101; C01B 35/04 20130101; C23C 16/38 20130101; C23C
10/08 20130101; C04B 2235/3843 20130101; C04B 2235/80 20130101;
C04B 35/62897 20130101; C04B 2235/3804 20130101; H01L 39/2487
20130101; C04B 2235/404 20130101; C04B 35/76 20130101; C04B
2235/5244 20130101; C04B 2235/3206 20130101; C04B 2235/5264
20130101; C04B 2235/428 20130101; C04B 2235/3826 20130101; C04B
2235/5248 20130101; C04B 2235/422 20130101 |
Class at
Publication: |
505/500 ;
505/300; 252/500; 252/520.22 |
International
Class: |
H01L 39/24 20060101
H01L039/24 |
Claims
1. A method for producing doped boron, the steps consisting of:
introducing a boron.sub.:containing vapor into a reaction vessel;
introducing a dopant vapor into the reaction vessel to provide a
mixture of the dopant vapor and the boron-containing vapor; and,
heating the mixture to produce doped boron.
2. The method of claim 1 wherein the boron-containing vapor is a
hydrogen and boron trichloride mixture.
3. The method of claim 1 wherein the dopant vapor is titanium
tetrachloride vapor.
4. The method of claim 3 wherein the boron-containing vapor is a
hydrogen and boron trichloride mixture.
5. The method of claim 4 wherein the hydrogen and boron trichloride
mixture is a roughly stoichiometric mixture.
6.-20. (canceled)
21. The method of claim 1 wherein the dopant vapor is a hydrogen
and titanium tetrachloride mixture.
22. A method for producing doped boron, the steps consisting of:
(a) introducing a boron-containing vapor into a reaction vessel by
metering a flow of hydrogen and metering a flow of boron
trichloride vapor through the reaction vessel; (b) introducing a
dopant vapor into the reaction vessel by passing at least a portion
of the flow of hydrogen through a bubbler containing liquid
titanium tetrachloride; mixing the hydrogen/titanium tetrachloride
mixture emerging from the bubbler with the flow of boron
trichloride going to the reaction vessel to form a boron-containing
vapor/dopant-containing vapor mixture; and passing the
boron-containing vapor/dopant-containing vapor mixture through the
reaction vessel; and, (c) heating the boron-containing
vapor/dopant-containing vapor mixture in the reaction vessel to
produce doped boron.
23. The method according to claim 22 wherein a metered flow of
hydrogen at about 3.1 liters per minute and a metered flow of boron
trichloride at about 4.2 liters per minute are flowed through the
reaction vessel.
24. The method according to claim 22 wherein step (c) comprises the
step of providing a heated surface inside the reaction vessel to
heat the boron-containing vapor/dopant-containing vapor
mixture.
25. The method according to claim 22 wherein step (c) comprises the
steps of heating a silicon carbide fiber by electrical resistance
heating to a temperature of about 1100-1300 degrees Celsius and
passing said heated fiber through the reaction vessel in contact
with the boron-containing vapor/dopant-containing vapor mixture.
Description
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 11/937,092, filed on Nov. 8, 2007, which is a continuation of
U.S. application Ser. No. 10/989,803, filed on Nov. 17, 2004, which
relies for priority upon International Application No.
PCT/US03/20628 filed on Jul. 1, 2003, which claims the benefit of
U.S. Provisional Application Ser. No. 60/429,137, filed Nov. 26,
2002, the contents of which are herein incorporated by reference in
their entirety.
BACKGROUND OF THE INVENTION
[0002] It has been discovered that magnesium diboride is a
superconductor with a transition temperature of approximately 40 K.
Magnesium diboride can be made by the reaction of elemental
magnesium and boron. The result of this process is a fine powder
which is commercially available. Experiments on small crystals of
this material have demonstrated high current-carrying capabilities
at high magnetic fields, properties which could make MgB2 very
useful in applications such as magnetic resonance imaging (MRI)
where large powerful magnets are required. Magnesium diboride,
however is an intractable material with respect to the usual
drawing processes for forming the continuous wires required for
such applications.
[0003] Magnesium diboride wires have been formed by a
"powder-in-tube" process in which a tube of cladding material is
filled with the fine powder and the composite tube is then drawn to
smaller diameter. (S. Jin et al, high Critical Currents in
Iron-clad Superconducting MgB2 Wires, Nature, Vol. 410, 63(2001)).
This process is expensive and may not lead to optimum properties in
the fabricated wire.
[0004] Another approach to forming MgB2 wires has been to convert
boron filaments by reaction with magnesium vapor. Boron filaments
are formed in a continuous chemical vapor deposition (CVD) process;
100 micron diameter boron filaments on a 12 micron tungsten
substrate are commercially available in lengths exceeding several
kilometers. Segments of these filaments were reacted with magnesium
vapor in sealed tantalum tubes. (Canfield et al, Superconductivity
in Dense MgB2 Wires, Phys. Rev. Lett., Vol. 86, 2424 (2001)). The
filament segments retained the shape of wires after conversion to
MgB2, and exhibited good superconducting properties. However, the
resulting wires were fragile and difficult to handle.
[0005] One objective of the invention disclosed below is to form a
boron substrate which can be converted to magnesium diboride in
continuous wire form while still retaining both good
superconducting properties and good mechanical properties such as
handleability.
[0006] Another aspect of the superconducting behavior of MgB2 is
the effect of impurities. Impurity sites can enhance the
current-carrying capability of a superconductor by "pinning"
magnetic vortices; the restrained vortices allow the sample to
retain a zero electrical resistance. (Canfield and Bud'ko, Physics
World, 29, Jan. 2001.) Impurities which have been found useful for
enhancing the properties of MgB2 include magnesium oxide, carbon,
silicon carbide and titanium diboride.
[0007] Another objective of this invention is to provide a
continuous boron substrate doped in a controlled manner by chemical
vapor deposition with atomic species which will, upon conversion of
the boron to MgB2, form "pinning" sites which will enhance the
current-carrying capability of the resulting superconductor.
SUMMARY OF THE INVENTION
[0008] In this invention, chemically doped boron coatings are
applied by chemical vapor deposition to silicon carbide fibers;
these coated fibers are then exposed to magnesium vapor to convert
the doped boron to doped magnesium diboride. The silicon carbide
fibers are the commercially available SCS-9 or 9A (nominal 3 mil
diameter) or SCS-6 (5.6 mil diameter). These silicon carbide fibers
exhibit high mechanical properties with tensile strength typically
in excess of 500 kpsi and Young's modulus in excess of 50 mpsi. The
SCS fibers have a carbonaceous surface layer which enhances the use
of the fibers in composite applications. Silicon carbide fibers can
also be produced without a carbon-rich surface layer. The
chemically doped boron coatings are produced by the controlled
addition of a dopant vapor to the gas stream normally used to
deposit boron. In this way the concentration of the dopant in the
coating can be controlled. For example, addition of titanium
tetrachloride vapor to the roughly stoichiometric hydrogen and
boron trichloride mixture normally used to deposit boron will
result in the deposition of boron doped with titanium diboride, and
the concentration of the titanium diboride can be controlled
through the vapor pressure of titanium tetrachloride. When the
(B/TiB2)-coated SiC is then exposed to magnesium vapor at high
temperature, the result is a robust SiC fiber coated with magnesium
diboride doped with titanium diboride.
[0009] Another useful dopant for magnesium diboride is magnesium
oxide. This can be produced by adding controller amounts of B3O3Cl3
to the gas stream used for boron deposition. The oxygen-doped boron
thus produced will convert to magnesium oxide-doped magnesium
diboride upon processing as above.
[0010] Silicon carbide has been shown to be a useful dopant for
magnesium diboride. The doped MgB2 was prepared in pellet form by
the reaction of a mixture of boron, magnesium and silicon carbide
powders in sealed tubes. Boron made by chemical vapor deposition
(by the hydrogen reduction of boron trichloride) can be doped with
controlled amounts of silicon carbide by the addition of metered
amounts of an organosilane such as methyltrichlorosilane to the
plating gas during the deposition process. Hence, a more convenient
method of forming a continuous SiC-doped MgB2 wire is a process
which includes forming a continuous SiC-doped boron substrate by
chemical vapor deposition and subsequently converting the substrate
to doped MgB2 by reaction with magnesium. The chemical vapor
deposition process provides a means of fabricating a continuous
substrate of controlled composition with a uniform dispersion of
the dopant.
[0011] Similarly, carbon as a dopant can be incorporated into
continuous MgB2 wires through a process as described above where a
hydrocarbon is added to the plating gas during boron deposition
instead of an organosilane.
[0012] Boron-containing coatings on silicon carbide are known
(Suplinskas et al, U.S. Pat. No. 4,481,257) but their application
is limited to enhancing the bonding in composites in which the
silicon carbide provides the reinforcement. The application to the
formation of superconducting wires is novel.
[0013] The doped boron coatings may be deposited on substrates
other than silicon carbide fiber. Tungsten wires, molybdenum wires
and carbon monofilament, for example, can be used for boron
deposition and could be used as well for the deposition of doped
boron. In this case, the specific mechanical property enhancement
due to the use of silicon carbide would not result, but the
improvement in superconducting properties such as superconducting
critical current density and upper critical magnetic field would
still be obtained after the coatings are reacted with magnesium to
form magnesium diboride. The conversion to magnesium diboride has
been illustrated by using the process of Caulfield et al, but other
means of converting the doped boron to a superconductor are
possible; for example, the continuous doped boron could be passed
through a batch of molten magnesium. The method used for the
reaction of the boron with magnesium is separate from the invention
described here.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Example 1
[0014] SCS-9 fiber, 3 mils in diameter, was passed through a
reactor normally used for the deposition of continuous boron fiber.
The continuous silicon carbide fiber enters the reactor at the top
through a mercury gas seal and electrode, and exits at the bottom
of the reactor through a similar seal/electrode. Fiber emerging
from the bottom of the reactor is taken up on a variable speed
take-up reel. The rate of fiber traverse through the reactor was 20
feet per minute. Reactant gases are admitted at the top of the
reactor and exhausted at the bottom. Metered flows of 3.1 liters
per minute of hydrogen and 4.2 liters per minute of boron
trichloride were passed through the reactor. The silicon carbide
was resistively heated by an electric current produced between
mercury gas seals/electrodes at the top and bottom of the reactor.
At a current of 200 milliamps, the silicon carbide fiber was heated
to 1100-1300 degrees Celsius. The hydrogen flow was then directed
to pass through a bubbler (coarse glass frit) containing liquid
titanium tetrachloride. The bubbler was immersed in an ice-water
bath; a thermocouple immersed in the TiCl4 read 3% C. The
hydrogen/titanium tetrachloride mixture emerging from the bubbler
was then mixed with the boron trichloride and passed through the
reactor. The diameter of the fiber emerging from the reactor was
approximately 3.3 mils compared to the 3 mil SCS-9 entering the
reactor. A sample of this coated fiber was collected on the take up
spool.
[0015] Examination of the collected sample showed a smooth uniform
adherent coating approximately 4 microns thick. Auger analysis of
the coating showed it to consist of approximately 90% boron and 10%
titanium. Sections of this fiber were sealed in tantalum tubes with
magnesium and heated to 950% C for one hour in the laboratory of
Doug Finnemore at Iowa State University by the method described by
Caulfield et al (loc.cit.). These converted fibers were
superconducting with a transition temperature of about 39% K.
Subsequent measurements showed a critical current density of 5
million amps per square centimeter at 5% K and a magnetic field of
0.1 Tesla. Similar measurements on superconductors made from pure
boron gave maximum values of approximately 600,000 amps per square
centimeter. The wires thus produced were handleable and could be
bent around a half inch diameter without breaking.
Example 2
[0016] Silicon carbide fiber, 3 mils in diameter, was passed
through the reactor described above. The rate of fiber traverse
through the reactor was 20 feet per minute. Metered flows of 3.1
liters per minute of hydrogen and 4.2 liters per minute of boron
trichloride vapor were passed through the reactor. The silicon
carbide fiber was resistively heated to approximately 1100 degrees
C. by a current of 162 milliamps. A portion of the hydrogen flow
could be diverted through a bubbler (coarse glass frit) containing
liquid methyltrichlorosilane at a temperature of 27-34 degrees C.
In a series of experiments as described in the table below, the
percentage of the total hydrogen flow that was diverted to the
bubbler was varied systematically. In all cases, smooth adherent
coatings 2-4 microns thick were formed on the silicon carbide. The
composition of the coatings was determined by Energy Dispersive
X-ray Analysis on a scanning electron microscope. The atomic
percent silicon found in each case is noted in the table. The data
demonstrates that controlled doping of the boron coatings was
accomplished.
TABLE-US-00001 Experiment Number % Flow through Bubbler Atomic %
Silicon 1 0 0 2 18 1.5 3 36 5.0 4 55 6.3 5 73 8.1
Example 3
[0017] Silicon carbide fiber, 3 mils in diameter, was passed
through the reactor described above. The rate of fiber traverse
through the reactor was 20 feet per minute. Metered flows of 3.1
liters per minute of hydrogen and 4.2 liters per minute of boron
trichloride vapor were passed through the reactor. The silicon
carbide fiber was resistively heated by the passage of electrical
current in the range 162-178 milliamps as indicated in the table
below. A metered flow of methane gas in the range of 0-950 standard
cubic centimeters per minute (SCCM) could be added to the reactor
in addition to the hydrogen and boron trichloride. A series of
experiments was performed in which the current and methane flow
were varied as described in the table. In all cases, smooth
adherent coatings 2-4 microns thick were formed on the silicon
carbide. The composition of the coatings was determined by Energy
Dispersive X-ray Analysis on a scanning electron microscope. The
atomic percent carbon found in each case is noted in the table. The
data demonstrates that controlled doping of the boron coatings was
accomplished.
TABLE-US-00002 Sample Number Methane (SCCM) Current (ma) Atomic %
Carbon 1 0 165 0 2 250 162 1.5 4 500 170 3.3 6 950 178 6.3
DOCUMENTATION
[0018] These experiments are described in detail in my laboratory
notebook entitled "B for superconductors" on pages 3-114.
* * * * *