Investigation of annealing
Just after
effects of ultra pure copper
T. Shigematsu, K. Morita, Y. Fujii, T. Shigi,
M. Nakamura and M. Yamaguchi
Department of Applied Physics, Faculty of Science,
Okayama University of Science, Ridai-cho,
Okayama, 700 Japan
Received 18 March 1992; revised 8 May 1992
In relation to construction of the copper nuclear
demagnetization stage, the residual resistance ratios
(RRR) of ultra pure (7N) copper plates after annealing
at various conditions were measured. Ultra pure cop-
per is so active that even a small amount of oxygen
diffused into the copper decreases the RRR value
considerably. However, if oxidized layers were
formed on the copper surface at an early stage of the
annealing, the RRR value increased up to 104 after
annealing.
Keywords: nuclear demagnetization stage; residual
resistance; annealing
Copper is used usually as a refrigerant material for
nuclear demagnetization stages, reaching sub-
millikelvin temperatures. In order to achieve as
low a temperature as possible and keep it as long as
possible, the following are important for the nuclear
stage: minimizing eddy-current heating and the time
dependent heat leak, and maximizing the packing factor
within the high field region. Recent nuclear stages I
have been slitted, thick solid copper bars to avoid vibra-
tional eddy-current heating, without using epoxy
material which introduces a time dependent heat leak.
More recently, piled copper plates have been employed
in order to increase the packing factor above 0.92`3.
Conventionally used OFHC copper contains ppm
orders of magnetic impurities which will cause time
dependent heat leaks ~. As ultra pure copper plates (7N)
(Dowa Mining Co Ltd, 1-8-2 Marunouchi, Chiyoda-ku,
Tokyo, Japan) have become commercially available, we
have investigated the best annealing condition to obtain
a high residual resistance ratio (RRR) value. These data
are necessary for construction of the nuclear stage.
Experiments
The 7N copper plate samples were 1 mm thick and
70 mm long × 50 nun wide, and were machined as shown
in Figure 1 for four-terminal resistance measurement.
0011- 2275/92/100913-03
© 1992 Butterworth Heinemann Ltd
The total length of current path was about 1 m.
the machining, the RRR value was 1900 (see Table 1,
sample No 1). The samples were then annealed under
various conditions as shown in Table 1.
During the heat treatment of the copper nuclear stage,
insulator sheets had to be inserted between the
copper plates to prevent them from being welded to each
other by diffusion. So, we first examined the influence
of AI203 wool in the annealing process. Both surfaces
of a copper plate (sample No 2) were covered with
A1203 wool and pressed tightly by stainless steel plates
using screws. This sample and a bare copper sample
(sample No 3) were annealed together in a quartz tube.
The temperature was increased to 1200 K within 30 h
and this temperature was maintained for 50 h in an
oxygen atmosphere of 1 x 10 -4 Torr. After switching
off the heater of the electric furnace, the samples were
cooled to room temperature within 20 h. After this heat
treatment the RRR values were very much decreased to
10 (sample No 2) and 50 (sample No 3) respectively. In
order to examine the origin of these very low values, we
proceeded to anneal copper samples without insulator
coverage in different atmospheres.
Samples No 4 and No 5 were annealed in a vacuum
of 1 × 10 -5 Torr. The annealing time of sample No
4 was about four times longer than that for No 5, as
shown in Table 1. The RRR value of No 4 was much
larger than those of No 2 and No 3 but still lower than
before annealing. Since annealing for a long time in a
vacuum of 1 × 10-5 Torr decreased the RRR value, in
the case of sample No 6 the inside of the quartz tube
was purged with pure argon gas before annealing, which
resulted in a higher RRR value.
For samples No 7 and No 8, pumping and purging
with pure argon gas were repeated several times, then
pure argon gas was constantly flowed into the quartz
tube at 1 atm. Although both samples were annealed in
the argon gas with different flow rates, the surfaces of
both annealed samples No 7 and No 8 were black and
current terminal
voltage terminal
lmm~[~~--I-1
tl o 41 mm
k
[r-u
L
I- 70ram
Figure 1 Schematic drawing of the copper sample
Cryogenics 1992 Vol 32, No 10 913
Research and technical note

Table 1 RRR values and o x y g e n contents of ultra pure copper samples (7N) af t er various heat treatments

Heat treatment
Sample Oxygen content
No Atmosphere etc. Annealing temperature and time RRR (ppm)

Before annealing 1900 1 - 0

Pressed between AI203 wool, 1 x 10 -4 Torr 02 1 2 0 0 K, 50 h 10 8
1 x 10 -4 Torr O2 1 2 0 0 K, 50 h 50 25
1 x l O - S T o r r vacuum 1 2 0 0 K, 50 h 870 1 -0
1 x l O - S T o r r vacuum 1 1 9 3 K, 15 rain and 1 1 4 3 K, 1 2 h 2300 3
1 x 10 - s Torr vacuum, purging with A r before annealing 1 1 9 3 K. 15 min and 1 1 4 3 K, 12 h 3700 1 - 0
1 atm Ar(contaminated with air at the beginning), f l o w 8 2 3 K, 5 0 h 9800
rate 20 cm 3 m i n - 1
1 atm Ar(contaminated with air at the beginning), f l o w
rate 60 cm 3 min -1 8 2 3 K, 5 0 h 10500
9 1 atm very pure Ar, f l o w rate 6 0 cm 3 rain -1 1 1 9 3 K, 15 min and 1 1 4 3 K, 12 h 5300
10 Annealing No 9 again, 1 atm very pure Ar, f l o w rate 60
cm a rain -~ 8 2 3 K, 50 h 4900 1 - 0
11 1 x 10 -4 Torr O2 1193K, 15minand 1143K, 12h 620
12 1 atm very pure A r w i t h a Ti mesh. f l o w rate 1 cm 3
min - t 1 1 9 3 K, 15 min and 1 1 4 3 K, 12 h 6700
13 Pressed between AI203 wool, 1 atm very pure Ar, f l o w
rate 6 0 c m 3 m i n - 1 1193K, 15minand 1143K, 12h 1500 1 -0
14 Pressed between greened-SUS a plates, 1 atm very pure
Ar. f l o w rate 6 0 cm 3 min -1 1193K, 15minand 1143K, 12h 1100 1 - 0
15 Loosely pressed between greened-SUS a plates, 1 atm
v e r y pure At, f l o w rate 6 0 cm 3 min -1 1193K, 15minand 1143K, 12h 1700 3

aSurface-oxidized stainless steel

peeled off easily. We noticed that the argon gas was con-
taminated with air while I atm argon gas was filled after
pumping. However, the RRR values were about 104,
which were the highest among all the annealed samples.
After repairing the argon flow line to be vacuum-
tight, sample No 9 was annealed in a very pure argon
gas flow (5N) at 1 atm. The resultant RRR value was
about a half of those of samples No 7 and No 8. This
sample was annealed again at 837 K for 50 h (sample
No 10), but the RRR value was not increased. From the
above experiments, it can be assumed that the oxygen dif-
fused into copper became the main scattering centre for
conduction electrons at low temperatures. To confirm
this assumption, we annealed sample No 11 in an
oxygen atmosphere of 1 x 10 -4 Torr for 12 h, and
obtained a low RRR value.
Then sample No 12 was annealed together with a
titanium mesh as a getter for oxygen contained in very
pure argon gas or out-gassed from the quartz tube etc.
A higher RRR value than that for sample No 9 was
obtained.
The next samples were annealed together with
insulator sheets in a flowing very pure argon
atmosphere. For sample No 13, A1203 wool was
pressed on the copper surfaces as for sample No 2. For
samples No 14 and No 15, greened stainless steel plates
were used instead of Al203. The former was pressed
tightly and the latter loosely. The RRR values of these
three samples were not so different and slightly smaller
than the value for sample No 1,
The resistance measurements were done by increasing
the current by 1 A from - 1 0 A to 10A at 300 K and
4.2 K. The I--V characteristics were linear within 1%.
The resistivity of sample No 9, for example, was
1.6 x 10 -6 fl cm at 300 K and 3.0 x 10 -~° fl cm at
4.2 K.
The oxygen contents of the annealed samples were
analysed chemically. The results are shown in Table 1.
Although the sensitivity of this method was about
1 ppm, the accuracy was reduced to about 3 ppm owing
to the readsorption of oxygen. Anyway, it is clear that
samples No 2 and No 3 contained more oxygen that the
others.
Discussion
The sample annealed in the oxygen atmosphere of
1 x 10 -4 Tort had the lowest RRR value. The RRR
value increased step by step as the atmosphere was
changed to 1 x 10 -s Torr vacuum, 1 atm pure argon
gas and 1 atm pure argon gas with a titanium getter.
These results show that even a very small amount of
oxygen diffuses into the ultra pure (7N) copper and
decreases the RRR value considerably.
However, the annealing temperature and time do not
seem to have as much influence on the RRR value as
oxygen does.
In the case of OFHC copper (4N), the RRR value
increases by annealing in an oxygen atmosphere of about
10- 4 Torr I - 6. Oxygen diffuses into impure copper and
oxidizes the magnetic impurities selectively. The
oxidized magnetic impurities lose their effectiveness for
scattering of conduction electrons. However, the ultra
pure copper is so active that oxygen diffuses into pure
copper and makes an interstitial alloy. The oxygen
results in scattering centres of conduction electrons.
Samples No 7 and No 8, whose surfaces were heavily
oxidized in the annealing process, had very high RRR
values. This can be explained as follows. If the copper
surface is oxidized heavily at the first stage of annealing,
oxygen cannot diffuse into copper as the energy barrier
of the oxidized layer is too high.

914 Cryogenics 1992 Vol 32, No 10


Conclusions
The R R R values of ultra pure (7N) copper were
measured after the annealing in various atmospheres.
Even a very small amount o f oxygen diffused into ultra
pure copper decreased the RRR value considerably.
However, if the copper surface was oxidized heavily at
the first stage of annealing, the RRR value increased up
to 10 4, probably because the oxidized layer prevented
oxygen f r o m diffusing into the copper.
Acknowledgements
The authors would like to thank Dr H. Hiraoka of
O k a y a m a University of Science for valuable comments
and Mr T. Yotsuya o f Osaka Prefectural Industrial
Technology Research Institute for analyses of the
oxygen content of the annealed copper samples. This
work was partly supported by O k a y a m a Ceramics
Research Foundation.
Research and technical note
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