LOW-Jc APPLICATIONS OF HIGH-Tc SUPERCONDUCTORS

F. Pavese,1 M. Bianco,2 M.Itoh,3 D.Giraudi,1 and K.Mori 3

1 CNR, Istituto di Metrologia "G.Colonnetti" (IMGC)

Torino 10135, Italy
2 RTM Institute
Vico Canavese 10060, Italy
3 Dpt. Electronic Engineering, Kinki University
Osaka 577, Japan

ABSTRACT

Several low critical-current applications of high-Tc superconductors (HTS) are possi-

ble, some of which already have industrial potential. Three of them are presented, which
make use of YBCO or BiSCCO extended thick (> 50 µm) films sprayed on metallic sub-
strates by means of the HVOF thermal spray technique. The more extensively studied, so
far, is magnetic shielding for cancellation of the magnetic field inside enclosures. With a
single layer, attenuation factors of the external magnetic field greater than 104 are obtained
for static magnetic fields, much better than using multiple layers of conventional high-
permeability materials. The maximum shielded field of ≈ 1•10-4 T can easily be improved
to ≈ 0.1 T by using a secondary shield made of low-cost ferromagnetic materials. A second
application, under development, is thermal shielding, taking advantage of the fact that be-
low Tc a superconducting surface reflects most of the thermal radiation. Heat transfer can
be reduced to levels comparable with those obtained with the best multilayer insulation
techniques. A third application is for magnet current leads, with currents < ≈100 A. In this
case, the powder-in-tube technique or the use of bulk materials is exceedingly costly and
the current density provided by these techniques needlessly high. The use of low-conduc-
tivity metal strips coated with superconducting thick films allows one to better compromise
performances and costs. A review of the state-of-the-art is provided and some of the latest
results are reported.

INTRODUCTION

After the discovery of the high critical temperature superconductors (HTS), much re-
search was devoted to large applications involving high currents and high current densities,
where the starting material is bulk. Alternately, some small scale applications have been
developed too, like SQUIDs and telecommunication micro devices, with the use of thin
films (< 1 µm). Thick-film (> ≈ 20 µm) applications have received impetus, however, be-
cause the technology of thick films on metallic substrates is not yet developed enough. For
this reason, some applications that can only use thick films so far have not received much
consideration. Among them, magnetic shielding (where shielding is thickness dependent)
and related applications, and thermal shielding (where the thickness must be higher than the
radiation penetration depth), when the fabrication also involves large surface areas. There
are other cases where bulk or thin films are used inefficiently, for example, in the fabrica-
tion of magnet current leads for moderate currents. On the other hand, thick films can be
fabricated only with a limited number of economical techniques. Plasma spray is the one
more often used, with insufficient results. Other techniques, like electrophoresis or ink lead
to low-density layers: screen printing has sometimes been added to improve density, but it
increases cost as well. Silver or ceramics were the substrates used with these techniques,
both involving considerable problems (thermal expansion mismatch and cost). However,
the interest on thick films is rapidly growing, especially due to economical reasons. The
number of studies and publications on this subject is increasing, extending beyond the
technique of the “thermal spray” family to chemical techniques (like those of the CVD
family) or physical techniques (like the new IBAD one). The use of the HVOF technique
for HTS thick-film production has been reported rarely; the only systematic studies have
been initiated by some of the authors.
First, magnetic shielding will be reviewed shortly, since it is, by far, the more deeply
explored with the aim of cancelling the magnetic field inside enclosures with walls coated
by an HTS material.
Secondly, thermal shielding will be illustrated, a new application that takes advantage
of the fact that below Tc a superconducting surface completely reflects the thermal radia-
tion. Very low emissivity values can be obtained, which would allow saving much refrig-
eration power in large applications.
Finally, design principle for using thick films for magnet current leads, when current
can be lower than ≈100 A, are presented in the last section.

ELECTROMAGNETIC SHIELDING

The subject of electromagnetic shielding by using high-Tc superconductors has re-

cently been extensively treated in a number of papers.1-3 Making an "electromagnetic
vacuum" will be considered only, where the techniques based on the new materials are
almost mature for applications such as biomedical measurements of weak magnetic fields,
electromagnetic compatibility measurements and electronic security.
The traditional approach makes use of high-permeability materials for dc fields and
low frequency fields (high electrical conductivity materials for higher frequencies). They
have limited shielding capabilities, especially below 10 Hz: a double-layer magnetic shield
shows a typical shielding factor S < 100 for medium-large shields. A larger number of lay-
ers would give somewhat better results, but other difficulties arise. The cost of these cham-
bers is extremely high. Low-Tc superconducting materials behave much more efficiently,
allowing values of S > 104, but only aiming at applications where liquid helium can be used
conveniently. With high-Tc superconducting materials the measured values of the shielding
factor are consistently higher than 104 for small-to-medium size cylinders.
Magnetic shielding differs in three main respects from most of the other applications
of superconductors: a) the application requires bi-dimensional isotropic characteristics; b)
values of Jc as low as 100 A cm-2 can be sufficient; c) bulk material is generally unneces-
sary and thin films are not suitable.
Therefore, contrary to most other applications, (a) there is little or no advantage at all
in optimising Jc in one direction, (b) the thickness t is the main relevant parameter, since in
first approximation (Jc = const)4 the shielding factor is proportional to t but there is no ad-
vantage in increasing it above a few tenths of a millimetre (per layer), since for larger val-
ues an exponential dependence for Jc(B) 5 comes into effect. Consequently, thick films are
well suited for this application.
 4.2 K 50 K 64 K 77 K
1.4 5.6
YBCO YBCO +1 +2
8 only iron cylinders
1.2

1.0 6
3.6
0.8
BiPbSCCO 2.4
4
0.6
2
0.4 BiSCCO
1
0.2 0

0
0 20 40 60 80 100 1 10 100
T /K Bext / mT

Figure 1. Increase of Jc when lowering Figure 2. Increase of the maximum shield

temperature. field when using a hybrid
(ferromagnetic + HTS) shield.

The results in the literature consistently show that the maximum shielded values are
in the range Blim ≈ (1—10)•10-4 T for a single layer of YBCO (lower values) 6-7 or
BiSCCO (higher values), and that this value can easily be improved to > 0.1 T by using
external shields of low-cost ferromagnetic materials, like soft iron or similar materials.8-9
A single soft iron shield increases the value of Blim up to ≈ 50 mT. Another way to easily
increase Blim is to cool the shield below 77.3 K (Fig.1). It is not necessary to reach helium
temperatures, where low-Tc materials are available: by cooling down to the minimum tem-
perature for liquid nitrogen, i.e., by using nitrogen slush, (≈ 64 K) Blim already improves by
a factor of 2.4 (for a ratio Blim(4.2 K)/Blim(77.3 K) ≈ 5.6. Ratio values larger than 10 have
been observed (Fig.2).2 Using an inexpensive one-stage refrigerator that can reach 50 K,
the gain is about a factor of 3.6. Values as low as Jc = 100 A cm-2 (typical, e.g., of poly-
crystalline YBCO) are still useful, contrary to most other applications, suggesting again the
use of thick films, which are also advantageous from an economic point of view.
On the other hand, thick films require a substrate, subjected to several constraints.
Ceramics are expensive and rigid. Silver is the best suited (see Fig.3) but has a large
thermal-expansion mismatch with superconducting ceramics, which drastically limits its
use. Technical substrates, such as stainless steel, contaminate the superconductor and
therefore require an efficient diffusion barrier (Fig.4).7, 10

1000000

100000

10000
S

1000

100

10

1
0 5 10 15 20 25
Bext / 10-4 T
 Figure 3. Typical shielding factor S = Bext/Bint obtained for B < Blim with a YBCO
thick film deposited with the HVOF technique on silver; Blim = 1.5 mT.

Figure 4. Cross-sections of a stainless steel tube with nickel-based buffer layer, coated with a single
thick YBCO layer. One small division = 10 µm; the black line delimiting the nickel layer
has been drawn as a visual aid.

Table 1. Selection of possible techniques from the viewpoint of the fabrication of superconducting shields.

Technique Pros Cons

Bulk ceramic parts Self-supporting. Limited size. Very thick (1.5–

>10 mm depending on size).
Very heavy. Very expensive.
Electrophoretic coating Small/medium modules. Low deposition rate. Low den-
Silver substrate (thin-sheets). sity thin film. High temperature
sintering and oxygenation re-
quired.
R Laser ablation deposi- No subsequent heat treatment Low deposition rate. Thin
e tion required. films. Small targets. Expensive
q Laser deposition Low deposition rate. Very criti-
u cal parameters. Expensive.
i Critical high temperature
r sintering and oxygenation
e required. Small modules.
Sputtering No subsequent heat treatment Low deposition rate.
deposition required. Thin films. Expensive.
Plasma spray Thick-film, large-area coatings. Very high process temperature.
(atmospheric pressure) Very high productivity. Critical high-temperature
deposition Structural materials as sub- sintering and oxygenation
strate. Suitable for multilayer- required.
ing. Stoichiometric problems.
Plasma spray Thick films. Very high produc- Very high process temperature.
(low pressure) tivity. Critical high-temperature
deposition Structural materials as sub- sintering and oxygenation
strate. required. Stoichiometric
Suitable for multilayering. problems. Expensive for large
modules.
s Hypersonic spray Thick-film, large-area coatings High-temperature sintering and
u (HVOF) deposition with limited grain melting. oxygenation required
p Very high productivity. (uncritical).
p Medium process temperature.
o Very high density, non-porous
r layer. Good thickness unifor-
t mity. Structural materials as
substrate. Suitable for multi-
layering.
Metal cladding, multi- Unlimited layer thickness. Oxygenation problems of the
layers Better shielding properties. underneath layers. Higher pro-
duction costs.
Screen printing High productivity. Very good Relatively low density layer.
thickness control. Carbon contamination. In situ
Suitable for multilayering. reaction. High-temperature heat
treatment required.
Paint, ink coating High productivity. Good thick- Low density layer, except when
ness control. Inexpensive. used for laminates. In situ reac-
tion. High-temperature heat tre-
atment required. Contamination
possible from dispersing
media.

a Silver, nickel, stainless steel* (requires buffer layer against Cr and C contamination: silver, ceramic),
ceramic* (MgO, Al2O3, Zr2O3(Y) (compatible)). Asterisk indicates better thermal expansion matching.
Lower-melting supports could be used in cases where no high-temperature sintering nor pre-heating during
deposition is required.

The coating technique must have a very high productivity, to make the fabrication process
economical when the area to be coated is large. In this respect, only few techniques are
suitable for shield fabrication of medium-large size (Fig.5), such as plasma spray or the
continuous detonation spray technique (CDS, also called HVOF –high-velocity oxygen-
fuel).6 All require a high-temperature treatment, which constrains the size of the shield
component to that of the furnace. Table 1 lists and compares the advantages and
disadvantages of a number of available techniques: only very few of them are suitable for
the fabrication of extended thick films.

inner dewar working chamber

insulating
SC shield material
liquid
nitrogen
(77 K) inner
300 K
module
heater wall
300 K 300 K
super-
insulation outer
module
outer dewar wall heater
300 K

SC shield
refrigerating
shield shape: shield shape:
elongated cylinder cylinder with cap pipes on
(≈ 1:10) copper sheet
 a) b) c)

Figure 5. Types of magnetic shields depending on dimensions: inner shield temperature needs to be
ambient in biomedical applications. a) Small shield in one-piece, bulk; b) small shield
made of a one-piece short cylinder with a cap, bulk; c) flat module of a medium-large
shield, with the shield made of a thick film on a metallic substrate and with gas refrigeration.

A peculiar application based on shielding, which is under development at IMGC in

co-operation with the Istituto Elettrotecnico Nazionale (IEN), is even less demanding then
a shield for large applications: a cryogenic current comparator (CCC) –an instrument for
precision electrical metrology– based on high-Tc instead of the traditional low-Tc supercon-
ductors, where the use of the oxide superconductors is for a thick-film coating on the exter-
nal toroidal shield of the comparator –the magnetic field to be shielded being only the earth
field, or even less if used in a shielded room. 11 The comparator may also require, for the
windings, superconductor thin wires, requiring a very low Jc value, since the current circu-
lating in them is vanishingly small.

y /mm
15
vectors:B • 2• 1010

10

+
5

•
0

-5

-10

-15
-30 -20 -10 0 10 20 30
x /mm

Figure 6. External field generated by an electrical dipole placed in the indicated position
(cross and dot) inside the superconducting shield (L /w = 13) of a CCC.
The shield is toroidal with a cross section (shown) shaped as a narrow U of length L
and width w. Computations are done for a simplified geometry, the torus being
straightened and of infinite length both sides. The attenuation factor is ≈ 100.6L/w.
 THERMAL SHIELDING

BCS theory predicts a threshold before a superconductor can adsorb energy, so that
below this threshold no energy is adsorbed at all, i.e. the material is perfectly reflective.
The threshold is connected to the energy gap for electron states through the equation:

hc/λc = 3.5(1-T/Tc)1/2 kTc (1)

whence the cut-off wavelength λc. All wavelengths longer than λc are reflected. Evidently,
the higher Tc is, the lower the cut-off is, i.e., the more the radiation spectrum is reflected.
Also, it is clear the advantage to keep the reflective surface temperature as low as possible
below Tc.
Until recently the use of superconductors would have given little advantage: for example,
the use of Nb3Sn (Tc = 18 K) yields λc = 225 µm, which is lower than the average
wavelength (Wien's law) emitted by a blackbody for temperatures below ≈ 15 K only.
On the contrary, for the high-Tc superconductors (HTS) the cut-off wavelength is shifted to
much lower frequencies, where the maximum of the radiation energy density of a surface at
77 K occurs: 45.7 µm for YBCO and 37.4 µm for 2223-BiSCCO (and 27.4 µm for a 150 K
HTS). Figure 7 depicts this fact.
It has been calculated13, from the ratio of energies reflected by a 4 K superconducting
surface (ε = 1) and transmitted by a 77 K surface (ε = 1), that the reflection, which is only
2% for Nb3Sn, is 61% for YBCO, 75% for the 2223-BiSCCO and 92% for a 150 K HTS.
Therefore, with Tc = 110 K heat transfer between blackbodies at 4 K and 77 K is cut by
four, to ≈ 500 mW m-2. Then, using a reflective 77 K surface (ε = 0.03), heat transfer could
be reduced to ≈ 15 mW m-2.
Figure 8 shows the maximum amount of heat transfer between a surface with ε = 1 at
temperature T to a superconducting surface with Tc = 110 K at T = 4 K or 30 K. The
transfer can be even lower in the case of concentric cylindrical symmetry, where for
infinite-length cylinders of diameter de (at T) and di (at 4 K or 30 K) the reduction factor is
given by di/de ; or in the case of two opposite planes, where for infinite length, finite width
w and distance d the reduction factor is given by [ 1+ (d/w )2 - (d/w )]. Notice that raising
the superconductor temperature from 4 K to 30 K (which reduces the energy gap, thus
increasing the cut-off wavelength) about doubles the heat transfer. Finally, there is
advantage to cool the emitting shield from 77 K down to, say, 60 K: a gain of ≈ 4 in the
reduction of the heat transfer.
 W m-2 µm-1
T/K
1E+0
100
1E-1
1E-2 75
1E-3 60
1E-4
50
1E-5
1E-6 30
1E-7 4
1E-8
1E-9
1E-10
1E-11
1E-12
1 10 100 1000 10000
µm
Figure 7. Blackbody total radiation for a body at the indicated temperatures.
The cut-off wavelength is for a superconducting surface with Tc = 110 K at T = 4.2 K.

10

30 K
0,1

4K

0,01
0 20 40 60 80 100 120
Figure 8. Maximum heat transferred by a surface with ε = 1 at temperature T to a superconducting
surface with Tc = 110 K at T = 4 K or 30 K.

The HTS surface is reflective because of its superconducting state: therefore the re-
flective property does not depend on circulating current in the material. This is an excep-
tionally favourable condition for a granular material, since it means that grain connectivity
is not necessary.
On the other hand, only the superconducting surface fraction is reflective and its ef-
ficiency depends on the actual –and local– value of Tc. This is not a trivial requirement,
since it means that for 100% efficiency one needs a 100% "right" chemical phase of uni-
form quality. Thin layers of HTS are not well suited, since thickness should be comparable
with λc, or the emissivity of the underneath surface will start coming into account. The su-
perconducting surface must be exposed, otherwise the heat deposition will occur on any
non-HTS portion of the surface: however, one could take advantage of the relatively long
wavelengths of the relevant radiation and make use, if necessary, of protective layers either
thin or transparent in the relevant radiation bandwidth.
The use of bulk HTS is obviously out of the question for this application. Since the
surface to be coated is generally large, the coating process must be cheap to be competitive
with existing techniques. Since a 30 µm coating accounts for a volume of 0.3 dm3 m-2, a
low density HTS material is better suited. Therefore, BiSCCO is much better than YBCO
for this application, for two reasons; i) higher efficiency because of higher Tc: 16% more
reflective; ii) thinner coating for the same efficiency: 18% shorter λc.
Among different coating techniques, those best suited for thin films are unsuitable or
exceeding costly for making thick films with high deposition rates. The ink and elec-
trophoretic technique require high-temperature sintering to anchor the powder to the sur-
face, process that also critically affects the final quality of the superconducting phase and
can be incompatible with some substrates (e.g. copper). Filled-resin paints have the advan-
tage of using the superconducting powder as-is; however, the filling factor –i.e., the surface
coverage– is certainly quite lower than unity (typically 60%). Much more important, the
superconductor is not exposed to the surface, but is embedded in a resin (ε ≈ 1) which acts
as an adsorber for the radiation. The high-productivity thermal spray methods generally are
best suited, though they too generally require a high temperature treatment to restore the
crystal structure to the material, that the high temperature during the spraying process will
damage or destroy.
Recently, the HVOF technique for spraying YBCO6 has been used to spray BiSCCO
provided by IRTEC-CNR14-15. The starting powder (Bi1.86Pb0.35Sr1.9Ca2.1Cu3.06Ox),
prepared by way of a solid state reaction, starting from a mixture of bismuth, copper and
lead oxides, strontium and calcium carbonates, contained 97% of the 2223-phase, ≈3% of
the 2212-phase, and only traces of the 2201-phase. The original powder has an average size
d50 = 5 µm; for the specific purpose, it was re-sintered and the fraction below 10 µm and
above 100 µm selected.
After spraying on a silver substrate, a 60 µm thick coating (compact and crack-free as
usual) still contained 87% of the 2223-phase, with the 2201-phase increased to 13% (and
traces only of the 2212-phase): however, the crystal phase was physically damaged, since
magnetic susceptibility measurements gave Tc < ≈ 50 K. At present, subsequent heat
treatments were able to recover only partially the amount of the 2223-phase, and Tc did not
increase sufficiently.

MAGNET CURRENT LEADS

The use of superconductors for bringing current to high-current cryogenic magnets is

one that was considered very soon after the development of the superconducting ceramic
fabrication technology and there is a broad literature on the subject. It allows to extend the
fraction of the cryogenic path of the current leads which does not contribute to the refrig-
erator load. For current leads operated in vacuum, the design depends essentially on the ge-
ometry and on the thermal conductivity of the assembly.
The superconducting part of the current lead takes often the form of a rod, soldered
both ends to metal bushes; a safety metal lead is put in parallel to the superconducting path
in case of quench.16 This design has some critical issues. Two very low resistance joints
between the superconductor and the end metal must be obtained, which is not trivial. The
addition of the safety lead partially compromises the lower thermal conductivity of the su-
perconducting ceramic. The use of a BiSCCO rod, as is often done, keeps the current den-
sity in the rod much lower than the critical one, with the bad use of much more expensive
superconducting ceramic than necessary; in addition fragility of the rod has eventually re-
sulted to be a bottleneck.
For current up to less than ≈ 100 A, it is possible to consider a better optimization of
both the design and the fabrication cost by using thick (> 100 µm) superconducting layers.
By this solution, which is presently under development at IMGC, the safety lead and the
metal-to-ceramic joints are integrated with the metallic substrate. Few tenths of a millime-
tre of superconducting material are sufficient, even with YBCO, to carry the current, mak-
ing the cost of the superconductor a small fraction of the total cost. The available high-pro-
ductivity spraying techniques (like HVOF) make the coating process an economic one.
Thermal conductance of the lead can easily be optimized taking also into account that Jc in-
creases toward lower temperatures, typically, by a factor of 5-10. Therefore, the lead cross-
section can accordingly be reduced –almost linearly– 10 times between the upper (60-70 K)
temperature and the lower (1.8 K) temperature. A sintered powder layer, also obtained with
the HVOF equipment, can be used for the metallic substrate, to reduce thermal conductivity
even when using materials such as pure nickel.16

Table 2. Design of magnet current leads using HTS thick films.

Design specs: B = null, I = 50 A; L (70—2 K) = 100 mm; thermal load P < 15 mW,
Tup = 70 K, Tlow = 2 K

HTS type 1 P/mW P/mW P/mW

substrate type 1 HTS only substrate only assembly
BiSCCO 1.6 10.1 11.7
AISI 304, bulk
YBCO 4.0 40.4 44.4
AISI 304, bulk
YBCO 4.0 ≈15 2 ≈20
sintered nickel
1BiSCCO: s = 2∞0.15 mm, J ≈ 1000 A cm2, J (4 K)/J (70 K) = 5.
c c c
Substrate: bulk AISI 304L strip, s = 0.3 mm, d = 5(@<4 K)/25(@70 K) mm.
YBCO: s = 2∞0.15 mm on each strip, J c ≈ 250 A cm2 , J c (4 K)/J c (70 K) = 5.
Substrate: 4 bulk AISI 304L strips, s = 0.3 mm, d = 5(@<4 K)/25(@70 K) mm each.
2 preliminary results.16 Thickness reduced to s = 0.1 mm.

Taking some CERN current-lead types17 as an example, it is possible to make calcu-

lations based on design parameters already achieved at IMGC. The BiSCCO rod of
Ballarino and Ijspeert17 –19.5 mm2 cross section (L = 100 mm) plus the associated 1.4
mm2 stainless steel wire (L = 822 mm)– is reported to have a thermal load of 12.5 mW.
As indicated in Table 2, a design making use of HTS thick films on stainless steel
strips allows to match the same specifications. The HTS itself accounts for less than 15% of
the total thermal conductance when using a bulk stainless steel strip for substrate: therefore
there is advantage to use the lowest thermal conductivity for the metal substrate, which can
even be achieved using sintered metal strips.
The reliable use of thick films instead of the bulk material also requires studies on the
long term stability of the coating with time before it can be considered for industrial appli-
cations. However, recent studies at IMGC showed that a suitable resin coating can be
painted on the HTS surface, stabilizing the YBCO characteristics with time.18

CONCLUSIONS

The magnetic shielding technique is essentially ready for the industrial market, espe-
cially when using the thick-film coating technique for the superconducting shield. The so-
lution provided for applications where the attainment of an "electromagnetic vacuum" is
the aim, the use of high-Tc superconducting materials provides by far superior results as
compared to the traditional use of high-permeability materials and a great practical simpli-
fication as regards to the use of low-Tc superconducting materials. Suitable commercial
BiSCCO and YBCO powders are already available with acceptable physical properties, and
at least a couple of high-productivity coating techniques are available. The thick-film coat-
ing technique on structural materials such as stainless steel has recently obtained consistent
results. In conclusion, this magnetic shielding technique is mature to scale up to the stage
of industrial-prototypes of medium-to-large size, where it is likely to show good competi-
tiveness with respect to the existing techniques.
The use of thick films for thermal shields and current leads is still being explored.
Calculations indicate the possibility of using to-date available materials and techniques.

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