• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SE535412C2
    申请号:SE0901106
    申请日:2009-08-21
    公开日:2012-07-31
    发明作者:Yoshitomo Inaba；Shigeru Kitagishi；Kunihiko Tsuchiya；Hironobu Izumo；Hiroshi Kawamura；Katsuyoshi Tatenuma；Kenichi Kato；Tuneyuki Noguchi
    申请人:Japan Atomic Energy Agency Org Under The Law Of Japan；
    IPC主号:
    专利说明:

    BRIEF SUMMARY OF THE INVENTION Many oxygen concentration detectors (sensors) have been proposed; they determine the oxygen concentration in the gas phase such as air by measuring the electromotive force over a ceramic membrane that is permeable to oxygen ions. important to be able to reduce the impact due to stress corrosion and cracking on the components that occur inside a nuclear reactor or in the pipes that are part of the cooling water system.
    Conventional oxygen concentration sensors present problems in terms of reliability in long-term use or resistance to thermal shock when used under the harsh operating conditions prevailing in high temperature and high pressure water.
    In view of these problems, the object of this invention is to propose a sensor for oxygen concentration and a measurement method which provides safe measurement without problems in long-term use or in terms of resistance to thermal shock when performing measurement under harsh operating conditions such as in water with high temperature and high pressure. Another object is to propose a method for producing an oxygen concentration sensor.
    In this invention, an oxygen concentration sensor is proposed which determines the oxygen concentration by measuring the electromotive force by means of a device in the form of electrodes arranged in this sensor which measures the electromotive force between the reference electrode and each of two electrodes and where the oxygen concentration sensor has a sensing device formed with a tablet-like shape by integral calcination. The invention also comprises a ceramic material which is permeable to oxygen ions, an insulator which is applied to one side of the ceramic material, an inner electrode 10 15 20 25 30 535 412 3 which consists of a mixture of a non-distributed metal which is used as a reference for the partial pressure of oxygen formed between the equilibrium during the thermal dissociation and the metal oxide where the mixture is embedded in the internal space between the ceramic material which is permeable to oxygen ions and the insulator and applied to one side of the ceramic material which is permeable to oxygen ions and in contact with this and an outer electrode which is exposed to the environment and is placed on the outer part of the ceramic material which is permeable to oxygen ions. In this invention, an oxygen concentration sensor is also proposed in which the sensing part is designed as a pillar.
    This invention proposes a method of manufacturing an oxygen concentration sensor which determines the oxygen concentration by measuring the electromotive force with an electromotive force measuring device mounted therein and which measures the electromotive force between a reference electrode and each of two electrodes and there the method comprises the following steps: applying an insulator to a side of a ceramic material which is permeable to oxygen; applying an internal electrode consisting of a powder mixture of a metal to be used as a reference with respect to the partial pressure of oxygen formed at the thermal dissociation equilibrium at the oxide of the metal in question and where the powder mixture is embedded in an internal space between the ceramic the material which is permeable to oxygen ions and the insulator and applied to one side of the ceramic material which is permeable to oxygen ions and in contact therewith; and applying an outer electrode facing the outside on the other side of the ceramic material which is permeable to oxygen ions and is then calcined integrally into a sensing element formed as a tablet.
    In this invention, a method is also proposed for designing the oxygen concentration sensor in which the sensing element is designed as a pillar. This invention further proposes a method of determining the oxygen concentration in high temperature, high pressure water by measuring the electromotive force between the inner electrode and the outer electrode which is in contact with high temperature water, and high pressure. The measurement is made with a sensing element that is placed in water with high temperature and high pressure.
    As mentioned above, the oxygen concentration sensor of this invention has a calcined tablet-shaped configuration. Therefore, this sensor can measure the oxygen concentration reliably and without problems during operation for a long time and with resistance to thermal shock when measuring under difficult operating conditions such as in water with high temperature and high pressure.
    BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an external view of the oxygen concentration sensor in an operating environment according to this invention.
    Fig. 2 is a longitudinal sectional view showing the internal structure of the oxygen concentration sensor in an operating environment according to this invention.
    Fig. 3 is a detailed view of Part A of Fig. 2.
    Fig. 4 is an elevated view of the front surface of the sensing element.
    Fig. 5 shows how the sensing element is arranged in the outer lining.
    Fig. 6 shows operating data from the oxygen concentration sensor according to this invention.
    Fig. 7 shows operating data from the oxygen concentration sensor according to this invention.
    Fig. 8 shows the method of manufacturing an oxygen concentration sensor according to an embodiment of this invention.
    DETAILED DESCRIPTION OF THE INVENTION The following is an explanation of an embodiment of this invention with reference to the drawings.
    Fig. 1 is an external view of the oxygen concentration sensor 100 in an operating environment according to this invention. Fig. 2 is a sectional view of the inner structure of Fig. 1. Fig. 3 is a detailed view of Part A of Fig. 2, and Fig. 4 is an elevated front view of the object depicted in Figs. 3.
    As can be seen from these figures, the oxygen concentration sensor 100 consists of an outer liner 1 of stainless steel as front part, an outer liner 2 of stainless steel as rear part integrally welded to the outer liner 1 and enclosing the rear part thereof and a flange 3 mounted on the outer liner 2. Inside the front part of the outer liner 1 a sensing element 10 is mounted; on its upper part a net 31 having a number of openings is provided.
    As shown in Fig. 3, the sensing element 10 is formed as a tablet by integral calcination: a ceramic substance 11 which is permeable to oxygen ions; an insulator 12 applied to one side of the ceramic blank 11 which is permeable to oxygen ions; an inner electrode 15 consisting of a powder mixture 14 of the metal to be used as a reference for the partial pressure of oxygen formed between the equilibrium of the thermal dissociation and the oxide of this metal and wherein the powder mixture 14 is embedded in the inner space 13 formed between the ceramic blank 11 which is permeable to oxygen ions and the insulator 12 and is applied to said side 40 of the ceramic blank 11 which is permeable to oxygen ions and in contact therewith; an outer electrode 18 facing the environment and located on the other side 41 of the ceramic blank 11 which is permeable to oxygen ions; and a reference electrode 19 whose outermost part on a supply line of Pt is embedded in the ceramic blank 11 which is permeable to oxygen ions. The outermost part of the reference electrode 19 can terminate either inside the ceramic blank 11 which is permeable to oxygen ions or on the boundary between the ceramic blank 11 which is permeable to oxygen ions and the insulator 12.
    The inner electrode 15 consists of the powder mixture 14 of a metal and the oxide thereof and a net 17 of Pt; the net 17 of Pt is applied to one side 40 of the ceramic blank 11 which is permeable to oxygen ions. In the example shown in Fig. 3, the inner space 13 is formed substantially within the insulator 12 and has a size adapted to accommodate the powder mixture 14. The insulator 12 is, for example, made of alumina.
    The inner space 13 is filled with a powder mixture, for example consisting of powders of: nickel - nickel oxide, copper - copper oxide, iron - iron oxide or cobalt - cobalt oxide. Other metals and their oxides can also be used.
    As a ceramic substance which is permeable to oxygen ions, solid solutions of orurite type such as calcium stabilized zirconia (ZrO 2 - CaO), yttrium stabilized zirconia (ZrO 2 - Y 2 O 3), calcium stabilized cerium oxide (CeO 2 - Y or solid solutions containing bismuth oxide (Bi2O3) or other sintered solids that are solid electrolytes permeable to oxygen ions can also be used.
    On the other side (ie the front side) of the ceramic blank 11 which is permeable to oxygen ions, a network of Pt is arranged so as to constitute the outer electrode 18. This outer electrode 18 is in contact with the outer environment characterized by high temperature water and high pressure (15 MPa, 300 ° C or higher) as in a nuclear reactor. To the network of Pt (ie the outer electrode 18) a conduit of Pt 21 is connected through the ceramic blank 11 which is permeable to oxygen ions and the insulator 12. To the network of Pt 17 which is connected to the inner electrode 15, the lead of Pt 22 is connected through the insulator 12.
    The ceramic blank 11 which is permeable to oxygen ions is arranged as follows: the insulator 12 is applied to one side of the ceramic blank 11 which is permeable to oxygen ions; the inner electrode 15 consisting of a powder mixture 14 of a metal to be used as a reference for the partial pressure of oxygen arising at the thermal dissociation equilibrium, and the oxide of the same metal. The powder mixture 14 is embedded in the non-space 13 which exists between the ceramic substance 11 which is permeable to oxygen ions and the insulator 12 on a side 40 of the ceramic substance 11 which is permeable to oxygen ions and in contact therewith; the outer electrode 18 exposed to the operating conditions is located on the other side 41 of the ceramic blank 11 which is permeable to oxygen ions; and the reference electrode 19, the outer part of the connecting line of Pt embedded in the ceramic blank 11 which is permeable to oxygen ions is integrally formed in one piece by means of a plasma sintering process and an apparatus for this purpose. By such a method, the sensing element 10 is formed which has a sintered integrated tablet-like shape. The sensing element 10 can then be formed into a rod-like shape to improve its strength.
    The geometry of the sensing element 10 is similar to a cylindrical tablet 10 to 20 mm in diameter and 5 to 10 mm thick.
    The sensing element 10 formed in this way is placed inside the outer lining 1 and fastened as shown in Fig. 5. During the application, the insulator 12 is held by another insulator 26 which is located in an inner space 24 inside the outer lining 1 and is locked by a locking means 25 which is fixed inside the inner space 23 on the inside of the outer lining 2. the insulator 26 is made of alumina. The Pt leads 21, 22 and 29 pierce the insulator 26 and the locking means 25 and pass through the inner space 23. The leads 27, 28 and 38 have been given insulating properties as they are inside the inner space 23 and are then joined to connection devices (not shown) and further connected to an electromotive force measuring device (not shown). In this way, the electromotive force between a reference electrode and each of two electrodes can be measured with this device for measuring electromotive force.
    Inside the inner space 23, Ar is filled with the pressure 10 to 15 MPa or you can instead fill water with high pressure. The inner space 23 can alternatively be designed with a structure of stainless steel, which means that the Pt lines 21, 22 and 29 must be designed with electrical insulation.
    On the outermost part of the outer liner 1 a net of porous stainless steel 31 is arranged with a small gap against the outer electrode 18. Through the holes there are led high temperature and high pressure water in to provide contact with the outer electrode. 18. The stainless steel mesh 31 is fitted to protect against the erosion which occurs due to the fate of high pressure water against the surface 30 of the ceramic blank 11 which is permeable to oxygen ions on the sensing element 10 where the surface 30 is exposed to the operating conditions. which means water with high pressure.
    A sensor for oxygen concentration 100 shown in Fig. 2 and which can withstand water with high temperature and high pressure has thus been produced.
    As shown in Fig. 2, the sensing element 10 and the insulator 26 are internally sealed within the inner space 24. Two pressure balancing holes 32 and 33 are provided on the outer liner 2. Alternatively, the inner space 23 can be made with a structure of stainless steel which means that the Pt lines 21, 22 and 29 must be provided with electrical insulation. The insulated conduits 27, 28 and 38 passing through the flange 3 are mineral insulated (MI) conduits 36, 37 and 38. 10 15 20 25 30 535 412 9 The oxygen concentration sensor 100 is given a size of 15 to 30 mm in diameter and 100 to 150 mm in length, however, other sizes do not affect the function.
    When the sensing element 10 is placed in water with high temperature and high pressure and has a design as indicated above, phenomena represented by the following chemical formulas occur in the case where a powder mixture of iron and iron oxide is used. When using other powder mixtures, a similar phenomenon occurs. srezoß zzFeso., + 1/2 02; p02 = sßix 10 * at 1ooo ° k Feao., 2 sFeao + 1/2 02; poz = 4.16 x 1o '° at 1ooo ° k The electromotive force is then measured according to the formula below.
    Emf (The oxygen potential in the reactor water) = {RT / zF} x | n (pO2 (internal) / pO2 (external)) ...
    Formula 1 above formula, R is a constant, T is the absolute temperature of the ceramic substance which is permeable to oxygen ions, pO2 (internal) is the partial pressure of oxygen on the electrode 17, pO2 (external) is the partial pressure of oxygen on the electrode 18.
    The value of the electromotive force Emf between the electrodes gives the value of pO2 (external) and measurement of the electromotive force thus makes it possible to determine the oxygen concentration in water with high temperature and high pressure.
    With the device for measuring the oxygen concentration 100 according to this invention, one can measure the partial pressure of oxygen, which gives an electromotive force between the electrodes and which arises over the separating ceramic substance which is permeable to oxygen ions, with a precision of one decimal; the greater the difference in the partial pressure of oxygen, the greater the electromotive force which gives increased sensitivity. Therefore, this sensor can measure the oxygen concentration reliably and without problems during operation for a long time and with resistance to thermal shock when measuring under difficult operating conditions such as in high temperature water and high pressure because the sensing element 10 is made of a sintered hard material . In this way, the electromotive forces between 38 which is the reference electrode and each of the two M1 leads 36 and 37 can be measured and transferred to oxygen concentration.
    As an example of measurements of the electromotive force Emf by means of the sensing element in high pressure water (5 to 15 MPa) and where the sensing element is heated to 300 ° C is shown in Fig. 6 (vertical axis: Electromotive force Emf [ /] , horizontal axis: Temperature [° C] The measurement results show that very small potentials of oxygen in high pressure water can be measured with good precision.It is clear that the electromotive force generated by the oxygen sensor is independent of the pressure, which is also evident from the above specified formulas.
    Another example of measurements of the electromotive force Emf in high pressure water and with the addition of 100 ppm hydrogen peroxide (H2O2) is shown in Fig. 7 (vertical axis: Electromotive force Emf [ /], horizontal axis: Time [min]) . The measurement results are consistent with the theoretical variation of Emf with respect to the concentration of H2O2 added; the same result was obtained with the addition of H 2 O; in concentrations ranging from 1 to 1000 ppm.
    An oxygen concentration sensor is manufactured by the following method, Fig. 8.
    The inner electrode is made of a mixture between a metal powder and an oxide powder. This mixed powder is installed in the internal space between the ceramic substance which is permeable to oxygen ions and the insulator. Furthermore, the reference electrode is embedded in the boundary area between the ceramic substance which is permeable to oxygen ions and the insulator (S1).
    The tablet-shaped surface of the ceramic substance which is permeable to oxygen ions is treated by the following procedure: 1 / A paste of a precious metal such as platinum, gold or silver or 2 / A ceramic electrode material with high conductivity such as oxides of metals in the lanthanum series or 10 535 412 1 1 3 / A metal mesh of a precious metal such as platinum, gold or silver is attached or 4 / Such a metal is evaporated or plated thereon (S2).
    These parts are joined together for the manufacture of the sensing element before sintering (S3).
    The joined parts (sensing elements) are applied to a plasma discharge sintering apparatus and sintered in one piece to an entire detail by means of this apparatus to form a sensing element such as in tablet or cylinder form (S4).
    The sensing element 10 within the oxygen concentration sensor 100 thus designed is exposed to high temperature, high pressure water to measure the electromotive force between the inner reference pole and the outer electrode which is in contact with high temperature and high pressure water to determine the concentration of oxygen in this water.
    权利要求:
    Claims (1)
    [1]
    An oxygen concentration sensor which determines the oxygen concentration by measuring the electromotive force by means of an electromotive force measuring device mounted therein and which measures the electromotive force between a reference electrode and each of two electrodes and wherein said oxygen concentration sensor has a sensing element having a tablet-like shape prepared by calcination in one piece: a ceramic substance which is permeable to oxygen ions; an insulator applied to one side of said ceramic blank which is permeable to oxygen ions; an inner electrode consisting of a powder mixture of a metal to be used as a reference for the partial pressure of oxygen arising from the thermal dissociation equilibrium, and the powder of said metal oxide and wherein said powder mixture is embedded in an internal space located between said ceramic material permeable to oxygen ions and said insulator and applied to said one side of said ceramic substance permeable to oxygen ions and in contact therewith; and an outer electrode which is subjected to the external conditions and is placed on the other side of said ceramic substance which is permeable to oxygen ions; and a reference electrode and an outer end of a lead of Pt embedded either inside said ceramic substance which is permeable to oxygen ions or in the boundary region between said ceramic substance which is permeable to oxygen ions and said insulator. . An oxygen concentration sensor according to claim 1 in which said sensing element has a rod-like shape. . A method of manufacturing an oxygen concentration sensor which determines the oxygen concentration by measuring the electromotive force by means of an electromotive force measuring device mounted therein and which measures the electromotive force between a reference electrode and each of two electrodes and wherein the method contains following steps: applying an insulator to a side of a ceramic substance which is permeable to oxygen ions, attaching an inner electrode consisting of a powder mixture of the metal to be used as a reference for the partial pressure of oxygen which occurs at thermal dissociation equilibrium and a powder of the oxide of this metal and in which said mixture is embedded in the inner space which exists between said ceramic substance which is permeable to oxygen ions and said insulator and applied to said one side of said ceramic substance which is permeable for oxygen ions and with contact therewith; applying an outer electrode opening to the outside of the outer surface of said ceramic substance which is permeable to oxygen ions; and a reference electrode and an outer end of a lead of Pt embedded either inside said ceramic substance which is permeable to oxygen ions or in the boundary region between said ceramic substance which is permeable to oxygen ions and said insulator and said device are calcined in one piece into a tablet-like sensing elements. A method of manufacturing an oxygen concentration sensor according to claim 3, in which said sensing element is shaped like a pillar. . A method of determining the oxygen concentration in high temperature, high pressure water by measuring the electromotive force that occurs between said inner electrode and said outer electrode in contact with high temperature and high pressure water by said sensing element within said oxygen concentration sensor. as described in claim 1 or claim 2 and which is located in water with high temperature and high pressure which constitute current operating conditions.
    类似技术:
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    同族专利:
    公开号 | 公开日
    JP5035853B2|2012-09-26|
    JP2010054233A|2010-03-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS5537920A|1978-09-11|1980-03-17|Toyota Motor Corp|Production of oxygen sensor element|
    JPS6244614B2|1979-12-26|1987-09-21|Toyota Motor Co Ltd|
    JP3736131B2|1998-08-25|2006-01-18|株式会社日立製作所|Sensor and plant operation method using the same|
    JP2000314717A|1999-04-28|2000-11-14|Kaken:Kk|Leakage detector|
    JP3801011B2|2000-12-07|2006-07-26|株式会社デンソー|Gas sensor element|
    JP2006084335A|2004-09-16|2006-03-30|Fujikura Ltd|Concentration cell type oxygen sensor|
    法律状态:
    2015-03-31| NUG| Patent has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2008217079A|JP5035853B2|2008-08-26|2008-08-26|Oxygen concentration sensor, method for forming the same, and method for measuring oxygen concentration in high-temperature high-pressure water|
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