JP2006053112A - Sensor probe using solid electrolyte - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sensor probe using a solid electrolyte good in user's convenience and easy to produce. <P>SOLUTION: A hydrogen/oxygen sensor probe 11 is constituted by incorporating two sensor probes same or different in kind among a hydrogen sensor probe 26 and an oxygen sensor probe 29 as unit sensor probes. Concretely, the hydrogen/oxygen sensor probe 11 is constituted by incorporating two sensor probes, that is, the hydrogen sensor probe 26 and the oxygen sensor probe 29 or by incorporating two same sensor probes. This sensor probe 11 is placed in a medium to be measured to measure the concentration of hydrogen or oxygen or the partial pressure of hydrogen or oxygen. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sensor probe using a solid electrolyte used for measuring a hydrogen concentration or an oxygen concentration or a hydrogen partial pressure or an oxygen partial pressure in a molten metal such as copper.

  Conventionally, copper has been used in Japan as an electric wire or a drawn copper product, but these electric wire and a drawn copper product are manufactured through melting and casting operations. In this melting and casting operation, when solidification defects such as pores occur, remelting is forced, which increases the energy intensity. It is known that hydrogen and oxygen dissolve together in molten copper. In particular, hydrogen dissolved in molten copper causes casting defects due to gas generation during solidification, and also remains in the material and causes deterioration of various characteristics. Therefore, the amount of hydrogen dissolved in the melting process can be monitored. It has been desired.

On the other hand, for oxygen in molten metal, technology has been established for in-line measurement of the dissolved amount in real time using a battery-type oxygen sensor probe using stabilized zirconia as a solid electrolyte, and it is effectively used in the copper melting process. ing. Regarding hydrogen in molten metal, development of a hydrogen sensor probe for molten copper using an oxide proton conductor is underway (see, for example, Non-Patent Document 1).
Resources & Materials '99 (Autumn Convention), Material Processing, D4-10, p. 124, (November 1 to 3, 1999, Japan Society of Resources and Materials)

  However, in the above-described prior art, the hydrogen sensor probe only measures hydrogen and the oxygen sensor probe only measures oxygen, and is one of the dedicated products, so it is inconvenient. In other words, if you want to measure the hydrogen concentration and oxygen concentration at the same time, or if you want to increase the reliability of the measurement of the hydrogen concentration or oxygen concentration, prepare a hydrogen sensor probe and an oxygen sensor probe, It was necessary to prepare two sensor probes. In addition, the hydrogen sensor probe and the oxygen sensor probe need to be separately manufactured as independent products, which is troublesome to manufacture. In addition, when other sensor probes such as a silicon sensor probe and a sulfur sensor probe are used, there are similar problems.

  The present invention has been made paying attention to such problems existing in the prior art. The object is to provide a sensor probe using a solid electrolyte that is easy to use and easy to manufacture.

  In order to achieve the above object, the sensor probe using the solid electrolyte according to the first aspect of the present invention includes a plurality of unit sensor probes each containing a reference substance in a solid electrolyte tube placed in a measurement target medium. It is characterized by being configured.

  A sensor probe using a solid electrolyte according to a second aspect of the present invention is the sensor probe according to the first aspect, wherein the plurality of unit sensor probes are configured by combining a plurality of different unit sensor probes or the same type of unit sensor probes. It is characterized by that.

  The sensor probe using the solid electrolyte of the invention according to claim 3 is the invention according to claim 1 or 2, wherein the plurality of unit sensor probes are a hydrogen sensor probe and an oxygen sensor probe. To do.

  According to a fourth aspect of the present invention, there is provided the sensor probe using the solid electrolyte according to the first or second aspect, wherein the plurality of unit sensor probes are a plurality of hydrogen sensor probes or a plurality of oxygen sensor probes. It is characterized by this.

According to the present invention, the following effects can be exhibited.
The sensor probe using the solid electrolyte according to the first aspect of the invention is configured by incorporating a plurality of unit sensor probes each containing a reference substance in a solid electrolyte tube placed in a medium to be measured. For this reason, in a measurement object medium, it can measure simultaneously with a plurality of unit sensor probes, and is convenient. Further, it is not necessary to separately manufacture a plurality of unit sensor probes, and parts other than the probes can be shared, so that the manufacture is easy.

  In the sensor probe using the solid electrolyte according to the second aspect of the present invention, the plurality of unit sensor probes are configured by combining a plurality of different unit sensor probes or the same type of unit sensor probes. For this reason, in addition to the effect of the invention according to the first aspect, different components can be simultaneously measured by different unit sensor probes, and measurement reliability can be improved by the same type of sensor probes.

  In the sensor probe using the solid electrolyte of the invention according to claim 3, since the plurality of unit sensor probes are a hydrogen sensor probe and an oxygen sensor probe, the hydrogen concentration or the hydrogen partial pressure and the oxygen concentration in the measurement target medium Alternatively, the oxygen partial pressure can be measured simultaneously.

  In the sensor probe using the solid electrolyte of the invention according to claim 4, since the plurality of unit sensor probes are a plurality of hydrogen sensor probes or a plurality of oxygen sensor probes, the hydrogen concentration or the oxygen concentration or the hydrogen partial pressure. Or the reliability of the measurement of oxygen partial pressure can be improved.

(First embodiment)
Hereinafter, a first embodiment of the present invention will be described in detail with reference to the drawings.
2A is a schematic front view showing the hydrogen oxygen sensor probe in the present embodiment, FIG. 2B is a schematic front view showing the probe and the holder in an exploded state, and FIG. 2C is a schematic rear view showing the computing unit. . As shown in these drawings, the hydrogen oxygen sensor includes a columnar hydrogen oxygen sensor probe 11, a bottomed cylindrical holder 12 that accommodates and holds the hydrogen oxygen sensor probe 11, and one end connected to the hydrogen oxygen sensor probe 11. The connection cable 13 is connected to the other end of the connection cable 13 via a connector 14.

  The hydrogen oxygen sensor probe 11 is immersed in a measurement target medium such as a molten metal such as copper, copper alloy, iron, or aluminum to measure the hydrogen concentration, oxygen concentration, hydrogen partial pressure, or oxygen partial pressure. Yes. The hydrogen oxygen sensor probe 11 incorporates two of the same or different sensor probes of the hydrogen sensor probe 26 and the oxygen sensor probe 29 as unit sensor probes. That is, the hydrogen oxygen sensor probe 11 is configured by incorporating two sensor probes of the same type, or by incorporating two sensor probes, the hydrogen sensor probe 26 and the oxygen sensor probe 29. When the hydrogen oxygen sensor probe 11 is used, the two hydrogen sensor probes 26 measure the hydrogen concentration or the hydrogen partial pressure, or the two oxygen sensor probes 29 measure the oxygen concentration or the oxygen partial pressure, or the hydrogen sensor. The probe 26 and the oxygen sensor probe 29 are configured to simultaneously measure the hydrogen concentration or hydrogen partial pressure and the oxygen concentration or oxygen partial pressure.

  The computing unit 15 is formed in a square box shape, and a temperature display unit 16 and a concentration or partial pressure display unit 17 are provided on the surface thereof. On the back surface of the calculator 15, a concentration / partial pressure display switching unit 18 and a power switch 19 are provided. Then, the calculator 15 calculates the hydrogen concentration or oxygen concentration based on the signal from the hydrogen oxygen sensor probe 11 or calculates and displays the hydrogen partial pressure or oxygen partial pressure.

  Next, the hydrogen oxygen sensor probe 11 will be described in detail. First, the case where the sensor probe includes the hydrogen sensor probe 26 and the oxygen sensor probe 29 will be described. FIG. 2 (a) is a front view showing the main part of the hydrogen oxygen sensor probe in a broken state, and FIG. 2 (b) is a side view when the cap is removed in the state of (a). As shown in these drawings, a cylindrical ceramic base 20 is disposed at the tip of the sensor probe, and a + -side strand 21 and a −-side strand 22 made of conductive wires are provided at substantially the center of the ceramic base 20. Are connected at the tip, and a thermocouple 23 formed in an arc shape is disposed. The thermocouple 23 is disposed in the quartz tube 24 and protected. The + side strand 21 is made of an alloy containing 13% by mass of rhodium in platinum, and the − side strand 22 is made of platinum.

  A hydrogen sensor probe 26 and a molybdenum electrode 25 are protruded from the thermocouple 23 so as to be almost the same height as the thermocouple 23. The hydrogen sensor probe 26 is protected by being covered with a protective sleeve 30. At a position opposite to the hydrogen sensor probe 26 across the thermocouple 23, an oxygen sensor probe 29 is provided so as to be almost the same height as the hydrogen sensor probe 26 and the molybdenum electrode 25.

As shown in FIG. 3, the hydrogen sensor probe 26 is configured such that a reference substance 32 functioning as a reference electrode is accommodated in a bottomed cylindrical solid electrolyte tube 31 placed in a measurement target medium. Α-alumina (Al ₂ O ₃ ) doped with 0.03 mol% of magnesia (MgO) is used as the solid electrolyte forming the solid electrolyte tube 31, and perovskite oxide (La _0.44 ) is used as the reference material 32. Sr _0.6 CoO ₃ ) is used. Note that the perovskite structure represents a specific cubic crystal structure. Further, copper as a measurement target medium serves as a measurement electrode, and an electrical signal is sent to the measurement electrode from a molybdenum electrode 25 as an external electrode.

On the other hand, the oxygen sensor probe 29 has basically the same structure as the hydrogen sensor probe 26 described above. As the solid electrolyte, zirconia (ZrO ₂ ) doped with 9 mol% magnesia (MgO) is used, and the mass ratio of chromium (Cr) and chromium oxide (Cr ₂ O ₃ ) is 9: 1 as the reference substance. These alloys are used.

  A copper cap 27 having a covered cylindrical shape is attached and fixed to the ceramic base 20 so as to cover the thermocouple 23, the hydrogen sensor probe 26, the molybdenum electrode 25, and the oxygen sensor probe 29. A through hole 28 is formed in the center of the tip of the cap 27 so that the outside and the inside of the cap 27 are communicated with each other through the through hole 28 in the molten copper constituting the medium to be measured.

  Next, a case where two hydrogen sensor probes 26 are provided as sensor probes will be described. As shown in FIG. 4A, in the structure of the sensor probe including the hydrogen sensor probe 26 and the oxygen sensor probe 29, The oxygen sensor probe 29 is changed to the hydrogen sensor probe 26. The other portions basically have the same structure as the sensor probe including the hydrogen sensor probe 26 and the oxygen sensor probe 29.

  Subsequently, a case where two oxygen sensor probes 29 are provided as sensor probes will be described. As shown in FIG. 4B, in the structure of the sensor probe including the hydrogen sensor probe 26 and the oxygen sensor probe 29, The hydrogen sensor probe 26 is changed to the oxygen sensor probe 29. The other portions basically have the same structure as the sensor probe including the hydrogen sensor probe 26 and the oxygen sensor probe 29.

Next, the principle of the hydrogen oxygen sensor probe 11 will be described.
As described above, as the solid electrolyte in the hydrogen sensor probe 26, proton conductive α-alumina doped with 0.03 mol% of magnesia is used, and a reference electrode made of perovskite oxide is provided on the inside thereof. Is provided. On the other hand, the measurement electrode is copper constituting the melt. When the hydrogen concentration or the hydrogen partial pressure in the medium existing on both sides of the solid electrolyte is different, the electromotive force E generated between the reference electrode and the measurement electrode is calculated based on the Nernst equation shown below.

但し、Ｅは理論起電力、Ｒは気体定数、Ｆはファラデー定数及びＴは絶対温度を表す。また、

However, E represents a theoretical electromotive force, R represents a gas constant, F represents a Faraday constant, and T represents an absolute temperature. Also,

は基準電極側における水素ガス濃度又は水素ガス分圧を表す。

Represents a hydrogen gas concentration or a hydrogen gas partial pressure on the reference electrode side.

は測定電極側における水素ガス濃度又は水素ガス分圧を表す。

Represents the hydrogen gas concentration or hydrogen gas partial pressure on the measurement electrode side.

  Furthermore, the value of A is a value represented by the following equation.

基準物質として、前述のペロブスカイト型酸化物（Ｌａ_0.4Ｓｒ_0.6ＣｏＯ₃）を用いると、

When the above-mentioned perovskite oxide (La _0.4 Sr _0.6 CoO ₃ ) is used as a reference material,

となり、水素ガスのような基準ガスが不要となる。

Thus, a reference gas such as hydrogen gas is not necessary.

  By using this Nernst equation, when one hydrogen gas concentration or hydrogen gas partial pressure and temperature are known, the other hydrogen gas concentration or hydrogen gas partial pressure can be calculated from the generated electromotive force. Accordingly, the function as the hydrogen sensor probe 26 can be achieved.

  The principle of the oxygen sensor probe 29 is basically the same as that of the hydrogen sensor probe 26. In the Nernst equation, the hydrogen gas concentration or the hydrogen gas partial pressure may be the oxygen gas concentration or the oxygen gas partial pressure.

  For example, when simultaneously measuring the hydrogen concentration and the oxygen concentration in the molten copper, a hydrogen oxygen sensor probe 11 having a structure including a hydrogen sensor probe 26 and an oxygen sensor probe 29 is prepared. Then, the hydrogen oxygen sensor probe 11 is directed toward the molten copper, and the cap 27 portion is immersed in the molten copper. At this time, the electromotive force (E) is measured by the hydrogen sensor probe 26 and the temperature (T) of the molten copper is measured by the thermocouple 23. Also, the hydrogen gas concentration on one side of the solid electrolyte is known. Therefore, in the calculator 15 of the hydrogen oxygen sensor, the hydrogen concentration in the molten copper is calculated based on the Nernst equation and displayed on the concentration or partial pressure display unit 17. The hydrogen partial pressure in the molten copper is also measured in the same manner, calculated by the calculator 15 and displayed on the concentration or partial pressure display unit 17. The temperature of the molten copper is measured by the thermocouple 23, calculated by the calculator 15, and displayed on the temperature display unit 16.

  On the other hand, the electromotive force (E) is measured by the oxygen sensor probe 29 and the temperature (T) of the molten copper is measured by the thermocouple 23. Further, the oxygen gas concentration inside the solid electrolyte pipe 31 is known. Accordingly, in the calculator 15 of the hydrogen oxygen sensor, the oxygen concentration in the molten copper is calculated based on the Nernst equation and displayed on the concentration or partial pressure display unit 17. The oxygen partial pressure is also measured in the same manner, calculated by the calculator 15 and displayed on the concentration or partial pressure display unit 17.

  Specifically, the results of measuring the hydrogen concentration and temperature in the molten copper are shown in FIG. The hydrogen concentration increased 10 seconds after the hydrogen oxygen sensor probe 11 was immersed in the molten copper, the hydrogen concentration decreased 20 seconds later, showed a substantially constant value at 1.3 ppm hydrogen concentration, and again after 35 seconds the hydrogen concentration again. The concentration decreased (marked with a circle in FIG. 5A). On the other hand, the temperature of the molten copper rose 10 seconds after immersing the hydrogen oxygen sensor probe 11 in the molten copper, showed about 1150 ° C. until 35 seconds, and then dropped [□ in FIG. mark〕. Therefore, when the hydrogen concentration in the molten copper shows a constant value of about 1.3 ppm, the temperature of the molten copper was about 1150 ° C.

  Moreover, the result of having measured the oxygen concentration and temperature in molten copper is shown in FIG.5 (b). The oxygen concentration increased 5 seconds after immersing the hydrogen oxygen sensor probe 11 in molten copper, the oxygen concentration decreased 9 seconds later, and showed an almost constant value at 2.3 ppm after 20 to 28 seconds [ A circle in FIG. 5B]. On the other hand, the temperature of the molten copper increased 5 seconds after the hydrogen oxygen sensor probe 11 was immersed in the molten copper, showed about 1100 ° C. until 28 seconds, and then decreased [□ in FIG. mark〕. Accordingly, when the oxygen concentration in the molten copper is a constant value of about 2.3 ppm, the temperature of the molten copper was about 1100 ° C.

  Thus, in the hydrogen oxygen sensor probe 11 of this embodiment, it is possible to simultaneously measure the oxygen concentration in addition to the hydrogen concentration in the molten copper with one probe. Therefore, when manufacturing a cast product from molten copper, it is possible to more accurately determine the possibility of occurrence of defects in the cast product.

  Next, FIG. 6 shows the results of measuring electromotive force and temperature in molten copper in the same manner as described above, using the sensor probe shown in FIG. 4A having two hydrogen sensor probes 26. As shown in FIG. 6, until 24 seconds after the hydrogen oxygen sensor probe 11 is immersed in molten copper, the electromotive force measured by the two hydrogen sensor probes 26 (marks ◯ and Δ in FIG. 6). ) Once increased and then decreased, and the electromotive force showed a substantially constant value of about 0.22 V between 24 seconds and 32 seconds. Thereafter, the electromotive force value of one hydrogen sensor probe 26 decreased. The two hydrogen sensor probes 26 showed substantially the same constant value, and the reliability could be improved. On the other hand, the temperature of the molten copper rose 12 seconds after the hydrogen oxygen sensor probe 11 was immersed in the molten copper, and showed about 1170 ° C. until 34 seconds (□ in FIG. 6). Therefore, when the electromotive force was stable at about 0.22 V, the temperature of the molten copper was about 1170 ° C.

  Next, FIG. 7 shows the results of measuring electromotive force and temperature in molten copper in the same manner as described above, using the sensor probe shown in FIG. 4B having two oxygen sensor probes 29. As shown in FIG. 7, the electromotive force (marked with a circle in FIG. 7) measured by one oxygen sensor probe 29 is about 16 seconds after the hydrogen oxygen sensor probe 11 is immersed in molten copper. The electromotive force gradually increased, and thereafter the electromotive force was approximately 0.7 V and showed a substantially constant value. Thus, the two oxygen sensor probes 29 showed substantially the same constant value, and the reliability could be improved. As for the electromotive force (marked by Δ in FIG. 7) measured by the other oxygen sensor probe 29, the electromotive force gradually increases until 10 seconds after the hydrogen oxygen sensor probe 11 is immersed in the molten copper. After that, the electromotive force was about 0.7 V and showed a substantially constant value. On the other hand, the temperature of the molten copper gradually increased until about 7 seconds after the hydrogen oxygen sensor probe 11 was immersed in the molten copper, and then showed a constant value at about 1170 ° C. (□ in FIG. 7). Therefore, when the electromotive force was stable at about 0.7 V, the temperature of the molten copper was about 1170 ° C.

According to the first embodiment described in detail above, the following effects are exhibited.
In the hydrogen oxygen sensor probe 11 of the first embodiment, two sensor probes of the same type or different types among the hydrogen sensor probe 26 and the oxygen sensor probe 29 are incorporated. For this reason, by using two sensor probes incorporated in the hydrogen oxygen sensor probe 11, the hydrogen concentration or hydrogen partial pressure and the oxygen concentration or oxygen partial pressure in the molten copper, which is the measurement target medium, are measured simultaneously, The reliability of measurement of oxygen concentration, hydrogen partial pressure, or oxygen partial pressure can be improved, which is convenient. Furthermore, it is not necessary to separately manufacture the hydrogen sensor and the oxygen sensor, and parts other than the probe can be shared, so that the manufacture is easy.

  The hydrogen oxygen sensor probe 11 incorporates two hydrogen sensor probes 26 or two oxygen sensor probes 29 as the same type of sensor probe. Therefore, determination can be made based on the measurement results obtained from the two sensor probes, respectively, and measurement results can be obtained with the remaining sensor probes even when one of the sensor probes becomes incapable of measurement. Therefore, the reliability of measurement of hydrogen concentration or oxygen concentration or hydrogen partial pressure or oxygen partial pressure can be improved.

Furthermore, since the hydrogen oxygen sensor probe 11 incorporates two sensor probes, the hydrogen sensor probe 26 and the oxygen sensor probe 29, the hydrogen concentration and oxygen concentration in the molten copper, which is the medium to be measured, are measured. It can be measured simultaneously.
(Second Embodiment)
Next, a sensor probe in which the oxygen sensor probe 29 and a manganese (Mn) sensor probe are combined will be described. The oxygen sensor probe 29 has the same configuration as the oxygen sensor probe 29 in the first embodiment. As shown in FIG. 8, the manganese sensor probe 33 as a unit sensor probe has a reference material 32 housed in a solid electrolyte tube 31 having a bottomed cylindrical shape, and a sub-electrode on a lower outer peripheral portion of the solid electrolyte tube 31. 34 is provided. The composition of the solid electrolyte and the reference material 32 constituting the solid electrolyte tube 31 is the same as that of the solid electrolyte of the first embodiment. The sub electrode 34 is made of manganese oxide (MnO) and is provided to improve the measurement accuracy of manganese.

  Then, by immersing the sensor probe in the molten iron, the oxygen sensor probe 29 is used to measure the oxygen concentration or oxygen partial pressure in the molten metal, and the manganese sensor probe 33 is used to measure the manganese concentration or manganese partial pressure in the molten metal. Can be measured simultaneously.

  Further, by providing a combination of the hydrogen sensor probe 26 and the manganese sensor probe 33 as sensor probes, both hydrogen and manganese in the molten metal can be measured simultaneously. Furthermore, by providing a plurality of manganese sensor probes 33 as sensor probes, the measurement accuracy of manganese in the molten metal can be improved.

It should be noted that the embodiments described above can be modified as follows.
In FIG. 1 (a), the oxygen sensor probe 29 can be disposed opposite to the proximity position on the hydrogen sensor probe 26 side from the thermocouple 23. In FIG. 4 (a), one of the hydrogen sensor probes 26 is connected to the thermoelectric sensor. The pair 23 can be disposed opposite to the proximity position on the other hydrogen sensor probe 26 side. Further, in FIG. 4B, one oxygen sensor probe 29 can be arranged opposite to the proximity position on the other oxygen sensor probe 29 side from the thermocouple 23.

  In FIG. 1A, the molybdenum electrode 25 can be disposed on the oxygen sensor probe 29 side from the thermocouple 23, and in FIG. 4A, the molybdenum electrode 25 is disposed on the hydrogen sensor probe 26 side from the thermocouple 23. Further, in FIG. 4B, the molybdenum electrode 25 can be disposed closer to the oxygen sensor probe 29 than the thermocouple 23.

  -As the thermocouple 23, the B type etc. prescribed | regulated to JISC1602 (1981) can be used. In the B type, the + side strand 21 is formed of an alloy containing 30% by mass of rhodium in platinum, and the − side strand 22 is formed of an alloy containing 6% by mass of rhodium in platinum.

-As said measuring object medium, the gas which exists in the upper space of a molten metal may be sufficient, for example.
As a reference material constituting the oxygen sensor probe 29, an alloy of 9: 1 mass ratio of nickel (Ni) and nickel oxide (NiO), 9: 1 mass of copper (Cu) and copper oxide (CuO) A ratio alloy or the like can be used.

A switch for holding the numerical value displayed on the calculator 15 can be provided, or a charging terminal can be provided.
・ As a sensor probe, use a chromium (Cr) sensor probe, a silicon (Si) sensor probe, a magnesium (Mg) sensor probe, an aluminum (Al) sensor probe, a sulfur (S) sensor probe, a copper (Cu) sensor probe, or the like. Can do. Two or more types of sensor probes selected from these sensor probes, the hydrogen sensor probe 26, the oxygen sensor probe 29, and the manganese sensor probe 33 can be used in combination.

  The sensor probe may be configured by combining three or more types of sensor probes, or may be configured by combining a plurality of the same type of sensor probes and different types of sensor probes.

Next, the technical idea that can be grasped from the embodiment will be described below.
The measurement target medium is a metal melt, the metal melt serves as a measurement electrode, and an external electrode that sends an electrical signal to the measurement electrode is shared by the hydrogen sensor and the oxygen sensor. A sensor probe using the solid electrolyte according to claim 3. When configured in this way, the configuration of the sensor probe can be simplified.

  The sensor probe using the solid electrolyte according to any one of claims 1 to 4, wherein the plurality of sensor probes are arranged to face each other at a proximity position. When comprised in this way, the measurement precision by each sensor probe can be improved further.

  The sensor probe using a solid electrolyte according to any one of claims 1 to 4, wherein the sensor probe includes a temperature measuring unit using a thermocouple. When comprised in this way, in addition to the measurement by each sensor probe, the temperature of a measuring object medium can be measured.

  The tip of the sensor probe is covered with a cap having a through hole, and the cap portion is configured to be immersed in a medium to be measured. A sensor probe using the solid electrolyte according to claim 1. When comprised in this way, while being able to protect a sensor probe with a cap, the measurement precision by each sensor probe can be improved.

(A) is the front view which fractures | ruptures and shows the principal part of the hydrogen oxygen sensor probe in embodiment, (b) is a side view when a cap is removed in the state of (a). (A) is a schematic front view which shows the hydrogen oxygen sensor in embodiment, (b) is a schematic front view which decomposes | disassembles a probe and a holder, (c) is a schematic front view which shows a calculator. Sectional drawing which expands and shows a hydrogen sensor probe or an oxygen sensor probe. (A) is a side view of a state in which the cap is removed with a hydrogen oxygen sensor probe having two hydrogen sensor probes, and (b) is a state in which the cap is removed with a hydrogen oxygen sensor probe having two oxygen sensor probes. Side view. (A) is a graph showing the relationship between the immersion time of the hydrogen oxygen sensor probe in molten copper and the hydrogen concentration and temperature; (b) is the immersion time of the hydrogen oxygen sensor probe in molten copper and the oxygen concentration and temperature; The graph which shows the relationship. The graph which shows the relationship between the immersion time of the hydrogen oxygen sensor probe provided with two hydrogen sensor probes in molten copper, an electromotive force, and temperature. The graph which shows the relationship between the immersion time of a hydrogen oxygen sensor probe provided with two oxygen sensor probes in molten copper, an electromotive force, and temperature. Sectional drawing which expands and shows a manganese sensor probe.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Hydrogen oxygen sensor probe, 26 ... Hydrogen sensor probe as a unit sensor probe, 29 ... Oxygen sensor probe as a unit sensor probe, 31 ... Solid electrolyte tube, 32 ... Reference material, 33 ... Manganese sensor probe as a unit sensor probe .

Claims (4)

A sensor probe using a solid electrolyte, wherein a plurality of unit sensor probes each containing a reference substance are incorporated in a solid electrolyte tube placed in a measurement target medium. The sensor probe using a solid electrolyte according to claim 1, wherein the plurality of unit sensor probes are configured by combining a plurality of different unit sensor probes or the same type of unit sensor probes. The sensor probe using a solid electrolyte according to claim 1 or 2, wherein the plurality of unit sensor probes are a hydrogen sensor probe and an oxygen sensor probe. The sensor probe using a solid electrolyte according to claim 1 or 2, wherein the plurality of unit sensor probes are a plurality of hydrogen sensor probes or a plurality of oxygen sensor probes.

Images