Superconductor technology: apparatus – material – process – Processes of producing or treating high temperature... – Coating
Reexamination Certificate
2000-12-13
2002-11-26
Kunemund, Robert (Department: 1765)
Superconductor technology: apparatus, material, process
Processes of producing or treating high temperature...
Coating
C505S700000, C148S030000, C148S525000, C148S537000
Reexamination Certificate
active
06486100
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to bulk superconductors and a novel seeding and growth process for preparing a bulk multi-domained superconducting material having strongly-linked low-angle domain boundaries.
BACKGROUND OF THE INVENTION
Since the discovery of high temperature oxide superconducting materials having critical temperatures that exceed the temperature of liquid nitrogen, there has been a concerted effort to utilize these materials for various applications. Although many applications are aimed at replacing conventional superconductors in wires and electronic devices, new applications using bulk materials also have been proposed. These applications include, for example, use in energy storage devices such as flywheels, use in current leads for superconducting magnets, and in magnetic bearings, bulk magnets, and magnetic resonance imaging machines (MRI).
For applications such as those noted in the proceeding paragraph, high temperature superconducting materials with large critical current density (J
c
) are required. One such high temperature superconducting material is a composite oxide of RE, Ba and Cu, and in particular, REBa
2
Cu
3
O
x
(wherein RE representing at least one of the following rare earth elements: Y, La, Sm, Nd, Eu, Gd, Dy, Ho, Er, Tm, Yb, or Lu).
One of the main factors that hinders the practical application of bulk high temperature REBa
2
Cu
3
O
x
superconductors is the limited size in melt-processed material of the oriented domains, or regions which contain primarily small angle grain boundaries and consequentially have properties similar to those of single crystals. Additionally, the J
c
of REBa
2
Cu
3
O
x
has been restricted by the presence of high angle boundaries which constitute weak links through which the current density drops dramatically in the presence of a magnetic field. Critical current density also decreases strongly with the angle between transport current and the strongly superconducting a-b planes. Thus, for these materials to be utilized in large scale practical applications, the entire specimen should consist of an oriented domain with its associated quasi-single crystalline characteristics.
Conventional melt growth and texturing processes have been developed to attempt to eliminate grain boundaries and exclude weak links, thereby increasing critical current density, field trapping capacity, and levitation force of high temperature superconductors. These enhanced properties are only exhibited within a single oriented domain less than 10 mm in size. Unfortunately, because nucleation is not controlled in conventional melt growth and texturing processes, the bulk samples formed from those processes generally consist of multiple misoriented domains with high-angle domain boundaries which are also limited in size. Although the J
c
within an oriented domain is generally on the order of 10
5
A/cm
2
, it decreases to values in the range of 10
2
-10
3
A/cm
2
when the current is required to flow through high-angle domain boundaries. To date, limitations in seed size, growth rate, and temperature processing range of high temperature superconductors have limited the sizes of single domains which can be produced by specialized processes such as seeding in the presence of chemical and temperature gradients. However, these processes require long processing time and are not suitable for mass production of superconductors.
Directional solidification techniques also have been developed for producing relatively long (<100 mm) single domained samples when the cross-sectional area is limited. When the cross section exceeds approximately 3 mm×3 mm, however, lateral temperature gradient causes formation of a superconductor that is multi-domained and misaligned.
Seeding has been proposed as a way to control grain orientation in the REBa
2
Cu
3
O
x
superconducting system. Seeding by single-crystalline SmBa
2
Cu
3
O
x
and NdBa
2
Cu
3
O
x
has been successful in producing YBa
2
Cu
3
O
x
domains of 30 to 50 mm in size. However, at least four main problems remain to be overcome before REBa
2
Cu
3
O
x
can be used in practical applications to obtain larger materials; these are 1) the size of the oriented domain, 2) weak links within the domain, 3) limitations with respect to the types of RE that can be used, and 4) impractical manufacturing time and cost. These problems would all be alleviated, to some degree, if larger seeds were available.
In conventional melt processing by small seeds of a few millimeters (mm) in diameter, the size of the REBa
2
Cu
3
O
x
that can be grown is limited as a result of grain impingement between the seeded domain and the neighboring domains which result from undesirable nucleation centers. Additionally, the degree of crystal perfection decreases, whereas the variation in chemical composition increases, as the growth front moves farther away from the seed. In other words, as the domain size increases, superconducting properties degrade. This decreasing quality of large single-domained high temperature superconductors has been confirmed by x-ray rocking curve analyses where the c-axis alignment is found to be degraded as the domain size increases. (see R. L. Meng et al.,
Physica C
232 (1994) 337).
Limitations in sample type have also been problematic. For example, YBa
2
Cu
3
O
x
can be produced by SmBa
2
Cu
3
O
x
seeds because its decomposition temperature is higher than that of YBa
2
Cu
3
O
x
, but NdBa
2
Cu
3
O
x
cannot be obtained in the same fashion. As a result, large single domained NdBa
2
Cu
3
O
x
, which has been shown to have more desirable properties than YBa
2
Cu
3
O
x
, cannot be obtained at this time.
In addition to the quality of the superconductors, the time and cost of manufacturing is also of concern. To obtain as large a domain as possible using small seeds, the cooling rate has to be extremely slow such that the manufacturing time of 20 mm size samples is typically well in excess of 100 hours. For samples on the order of 100 mm, the processing time would be measured in terms of weeks, if it were at all possible to fabricate samples of such dimensions.
To obtain large domains from small seeds, the growth front of the seeds must remain stable while proceeding for a large distance. High supercooling along the growth direction often leads to disorderly production of nuclei at the later stage of crystal growth resulting in multi-domained high temperature superconductors. To date, only when special modifications such as composition and/or sizable temperature gradients are employed can large single-domained REBa
2
Cu
3
O
x
be obtained. Although the domain size may be increased by these processes, the J
c
of such samples still is considerably smaller than that of small-domained specimens, indicating that weak links are still present in the apparent single-domained superconductors.
For further background information, please refer to the following publications:
1. K. Salama, V. Selvamanickam, L. Gao and K. Sun,
Appl. Phys. Lett.
54 (1989) 2352.
2. P. J. McGinn, W. Chen, N. Zhu, M. Lanagan and U. Balachandran,
Appl. Phys. Lett.
57 (1990) 1445.
3. V. Selvamanickam, C. Partsinevelos, A. V. McGuire and K. Salama,
Appl. Phys. Lett.
60 (1992) 3313.
4. K. Sawano, M. Morita, M. Tanaka, T. Sasaki, K. Kimura and K. Miyarnota,
Jap. J. App. Phys.,
30 (1991) L1157.
5. M. Hashimoto, M. Tanaka, M. Morita, K. Kimura, S. Takebayashi, H. Teshima, M. Sawamura and K. Miyamoto, in, in
Proc.
6
th US
-
Japan workshop on High Tc Supercond
., K. Salama, C. W. Chu and W. K. Chu, eds. (World Scientific, Singapore, 1994) p. 89.
6. D. F. Lee, C. S. Partsinevelos, R. G. Presswood, Jr. and K. Salama,
J. Appl. Phys.
76 (1994) 603.
7. R. L. Meng, L. Gao, P. Gautier-Picard, D. Ramirez, Y. Y. Sun and C. W. Chu,
Physica C
232 (1994) 337.
8. D. Dimos, P. Chaudhari and J. Mannhart,
Phys. Rev. B
41 (1990) 403.
9. A. Goyal, D. P. Norton, J. D. Budai, M. Paranthaman, E. D. Specht, D. M. Kroeger, D. K. Christen, Q. He, B. Saffian, F. A. List, D. F. Lee, P. M. Martin, C. E. Klabunde, E. Hatfield and V
Goyal Amit
Kroeger Donald M.
Lee Dominic F.
Akerman Senterfitt & Edison, P.A.
Kunemund Robert
UT-Battelle LLC
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