Solid State lonics 70/7 1 ( 1994) 606-609

SOLID
North-Holland STATE
IONUS

Development of long-term oxygen sensor in molten copper

using MgO-PSZ electrolyte
Wu Weijiang, Tang Shaohua, Hui Shiqiang and Liu Qingguo
Laboratory ofSolid State lonics, University of Science and Technology Beijing, Beijing 100083, China

A long-term sensor for molten copper was developed by using MgO-PSZ electrolyte tube. The reference electrode was pre-
sintered to avoid the appearance of a gap between the tube and reference electrode due to the shrinkage of reference electrode
powder at working temperature. Liquid sealing technique could be employed to improve the sensor long-term stability. The sensor
obtained is highly sensitive, simple in structure, easy to handle and low cost.

1. Introduction where P, is the oxygen partial pressure correspond-

ing to the melt and P2 that of the reference electrode.
Oxygen is one of the most active elements in the Therefore one can have
metallurgy of copper. An instant determination of
2FES AC’
the oxygen content in the copper alloy melt can en- lnaIol = RT (4)
sure the effective control of terminal of the oxidation
and reduction processes. It is mostly desired in the Eq. (4) shows that the oxygen activity in the copper
continuous casting process that the use of a contin- melt can be established with given values of the cell’s
uous oxygen determination and an in situ test of the EMF, E, temperature T, and the standard Gibbs free
changes in oxygen content may well guarantee the energy change AGO, accompanying the cell reaction.
quality of products. This necessitates the investiga-
tion and development of the oxygen sensor for con-
tinuous oxygen determination in copper melt. 2. Fabrication of the sensor
The present paper is aimed to develop an oxygen
sensor for the aforementioned purpose. Zirconia The tube is made of MgO-PSZ electrolyte. The
partially stabilized with magnesia is used as the elec- electrolyte tube was manufactured by sintering co-
trolyte. Materials for the fabrication of reference precipitated fine powders at high temperatures [ l-
electrode are the mixture of metal and metal oxide 3 1. The dimension of the tube is 5 mm in outer di-
powder. The cell structure is as follows: ameter, 33 mm in length and 1 mm in thickness, and
one end of the tube is closed.
FeCrAl, Me+MeOIZrOz(MgO) I [O],,, FeCrAl The tube containing 2.2 wt% MgO shows good
thermal shock resistivity and can be repeatedly put
(1)
into the copper melt for 5-7 times without the for-
The cell reaction is: mation of cracks. Additionally, since the content of
impurities of the electrolyte is very small, its elec-
Me+ [O],, =MeO . (2)
tronic conductivity is considerably low (at 12OO”C,
According to Nernst equation: P: = 1O-36 atm, lg P;=61.72- 143973/T) [4],
which makes the sensor suitable for continuous ox-
E=zlnF, (3) ygen determination.
2
In order to facilitate the sensor fabrication and de-

Elsevier Science B.V.

 Wu Weijiang et al. /Development of long-term oxygen sensor in molten copper 607

crease cost, solid state reference electrode is adopted.

Materials for reference electrode investigated by the
authors include Ni + NiO, Co + COO, MO + MOO,
Fe+FeO and Cr+ Crz03 and so on. As the protec- 1 ref.electrade
2 ZrOZ(MgO) tube
tive film on the surface of Crz03 is very dense, the
Cr + Cr203 electrode cannot be applied to the case of
copper smelting processes where the temperature is 5 hquid sealing
1100-l 300°C. On the other hand, the other four sys- 6 lead Eo-

tems of reference electrode materials have been found 7 sand

8 steel tube
very satisfactory to establish the oxygen content at 9 lead Eo+,Et+
working temperature in copper melt. Among them 10 lead Et-
11 ceramic tube
oxygen sensor with reference electrode made of Co,
12 quanztube
MO and Fe could survive a more than 8-hour test in
the laboratory, and the service time of Ni reference
electrode is relatively short, with an unstable EMF,
which may be due to the poor electric contact be-
tween the electrode and the inner wall of the tube, Fig. 1. The structure of long-tern oxygen sensor.
since the volume shrinkage of Ni+NiO electrode is
very great during sintering. tube. At the working temperatures, the formation of
In order to decrease the volume shrinkage because a liquid sealing layer will effectively prevent the in-
of sintering during measurement of the Co+CoO terference of the ambient oxygen.
reference electrode, pre-treatment has been taken in The weight of the reference electrode material can
the present investigation by the following means: be decreased to 0.15 g with the use of reliable sealing
mixing Co and Co0 according to weight proportion technique and sensors thus made have a long service
9 : 1 followed by sintering at 1200°C in Ar; powder life.
of 60 mesh is obtained from the sintered mixture. NiCr-Nisi thermocouple is used to measure the
This could decrease the volume shrinkage in service temperature. The lead wire used to contact with cop-
and result in a comparatively stable EMF. per melt is Fe-Cr-Al alloy which is resistive to the
The crux in continuous oxygen determination is corrosion of copper melt.
the sealing of the cell to prevent the interference of Cell reaction is
oxygen from ambient atmosphere. Therefore a well-
designed sealing method would be very important co+ [O]c,=CoO,
for the successful fabrication of a sensor. Even though AGO=-36190+13.1Tcal/mol
much cement is used to seal the end of the zirconia
tube, pores could not be thoroughly avoided at high and
temperatures which introduce the air into the ref- -7910+ 10.08E
erence electrode and lead to oxidation of Co to such k qcu] = T
+2.863,
an extent that the reference potential could not be
maintained. This will finally decrease the EMF and where E is in mV and T in K. The cell structure is
disconcert the measurement. Accordingly, a length- shown in fig. 1.
ened protective tube sealed with cement is used with
some Fe powder in its end as the oxygen getter, which
could prevent the interference of oxygen from the 3. Results and discussion
ambient air. Meanwhile, the decomposition of Co0
at low oxygen partial pressure established by Fe could The double cell sensors with Co+CoO and
also lead to an unstable EMF. In the present work, Ni + NiO reference electrodes are used simultane-
liquid sealing technique has been employed by put- ously to determine the oxygen contents in the copper
ting powder of micro-crystal glass into the quartz melt, with results listed in table 1.
 608 Wu Weijiang et al. /Development of long-term oxygen sensor m molten copper

Table 1
Measurement results of oxygen content in copper melt.

Test times Ref. electrode EMF(mV) a(ppm)

I co 190 517 \

2
Ni
co
Ni
96
199
98
519
566
570
L-
3 co 208 522
Ni 109 531
4 co 217 579
Ni 119 592
5 co 208 659
Ni Fig. 3. The measurement result of long-term oxygen sensor in flow
106 661
groove of Shanghai Smelter.

Fig. 2. The measurement result of long-term oxygen sensor in Fig. 4. The measurement result of long-term oxygen sensor in
laboratory. tundish of copper melt.

Table 1 shows that the EMF of the two reference
electrodes differ significantly, but the activities of
oxygen in the copper melt are in good agreement with
each other, with a relative deviation of less than 2%.
The reliability of long-term sensor could be tested
by means of expendable oxygen sensor. Fig. 2 is the
result obtained in the laboratory in a 1 kg copper
melt. Though it is difficult to control the oxygen con-
tent in the melt, the results are found to agree well
with those of the expendable oxygen sensor, which
indicates that the continuous measurements are
reliable.
Figs. 3 and 4 are the measurement results of cop-
per melt in flow groove and tundish of copper melt
on a production line in Shanghai Smelter. It can be
seen that the oxygen content in tundish changes with
that in the flow groove, with a difference of about
100 ppm. The difference corresponds to the atmo-
sphere and the time it remains at an adjusting con-
tainer between the flow groove and the tundish. The
oxygen content in tundish was considerably influ-
enced by the charcoal covering. The addition of new
charcoal leads to rapidly lowered oxygen content.
From these results it is concluded that the oxygen
sensor developed by the present investigation is reli-
able and highly sensitive for metallurgical
applications.
4. Conclusion
Oxygen sensor for long-term determination of ox-
ygen content in copper melt has been developed us-
ing MgO-PSZ as electrolyte and using solid state ref-
erence electrode. Liquid sealing technique could be
employed to improve the sensor long-term stability.
The sensor obtained is highly sensitive, simple in
structure, easy to handle and low cost.
 Wu Weijiang et al. /Development of long-term oxygen sensor in molten copper 609

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[2] S. An, T. Zhou, W. Wu and Q. Liu, Solid State Ionics 40/41
(1990) 750.
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[4] K. Huang, Y. Xia, W. Wu and Q. Liu, Solid State Ionics:
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1992 ) pp. 607-6 11.