JP5788291B2 - Reactor control rod - Google Patents

Description

  The present invention relates to a nuclear reactor control rod, and more particularly, to a nuclear reactor control rod suitable for application to a boiling water reactor.

  In the part where the structural members existing in water are close to or in contact with each other (hereinafter referred to as a gap), oxygen contained in the water that contacts the structural member is consumed, and there is abundant oxygen and oxygen concentration outside the gap. A battery is formed. For this reason, it is thought that a clearance gap becomes an environment where a corrosion reaction is easy to continue.

  In addition, in the gap portion between adjacent structural members made of stainless steel disposed in the nuclear reactor, three factors of radiation irradiation to the structural member, residual stress of the structural member, and gap overlap, so that corrosion in the structural member It becomes an environment where the reaction proceeds more easily.

  For example, since a nuclear reactor control rod that controls the reactor power is installed in the nuclear reactor and inserted into the core, the nuclear fuel material contained in the fuel assembly loaded in the nuclear reactor core is used in the sheath of the nuclear reactor control rod. Degradation of sheath due to irradiation of neutron and γ-ray generated by fission reaction and oxidation environment in contact with this sheath, tensile residual stress generated in sheath due to welding of sheath and tie rod, sheath and handle in manufacturing process, sheath and neutron Three factors of the crevice corrosion environment formed between the absorbing member and the hafnium elliptic tube overlap. For this reason, there is a concern that the space between the sheath and the hafnium elliptic tube is likely to cause crevice corrosion on the inner surface of the sheath of the reactor control rod.

  As a reactor control rod used in a boiling water reactor, a plurality of tubular hafnium elliptical tubes, which are neutron absorbing members, are arranged in a sheath to constitute a blade, and four blades are formed with a tie rod as a center. There are reactor control rods arranged in a letter shape. Such nuclear reactor control rods are described in, for example, JP-A-2-10299, JP-A-2002-71868, JP-A-9-61576, and JP-A-2002-71868.

  The conventional nuclear reactor control rod having a hafnium elliptic tube described in these publications has the following configuration. The nuclear reactor control rod has a cross shape in cross section and has a U-shaped sheath attached to the tie rod. The handle is attached to the upper end portion of the tie rod, and the lower support member is attached to the lower end portion of the tie rod. The upper end of the sheath is attached to the handle, and the lower end of the sheath is attached to the lower support member. An upper hafnium elliptic tube and a lower hafnium elliptic tube disposed below the upper hafnium elliptic tube are disposed in the sheath. An upper end portion of the upper hafnium elliptic tube is attached to a tongue-like portion provided on the handle. A lower end portion of the lower hafnium elliptic tube is attached to another tongue-like portion provided on the lower support member. A gap (for example, 0.1 to 0.2 mm) is formed between each hafnium elliptic tube and the inner surface of the sheath. The sheath has a plurality of openings that communicate with the gap.

  During operation of the reactor in which the reactor control rod is inserted into the core, cooling water flowing through the core is introduced through the opening into a gap formed between each hafnium elliptic tube and the inner surface of the sheath, It flows up in the gap. Each hafnium elliptic tube whose temperature has risen due to absorption of neutrons is cooled by the cooling water. That is, the hafnium elliptic tube is cooled by the cooling water. Boiling also occurs in the gap formed between the hafnium elliptic tube and the sheath inner surface. The width of this gap may change during operation of the reactor, which may hinder the flow of cooling water within the gap.

  In the vicinity of the core of a boiling water reactor, for example, an oxidizing agent such as oxygen and hydrogen peroxide is always generated by radiolysis of the cooling water, so that the cooling water contains an oxidizing agent such as oxygen and hydrogen peroxide. It is out. These oxidizers are also contained in the cooling water present in the gap formed in the reactor control rod sheath. The oxidizing agent contained in the cooling water takes electrons from the sheath surface and is finally reduced to water. In the gap between the reactor control rods, the amount of cooling water and the radiation absorbed dose of cooling water are small, so the amount of oxidant produced is small, and the oxidant is consumed by the reduction reaction, so the concentration of oxidant is low. It is lower than outside the gap (for example, outside the reactor control rod). For this reason, the reductive reaction in which the oxidant takes electrons from the sheath surface is small in the gap, and is large in other portions in contact with the bulk cooling water.

On the other hand, an oxidation reaction occurs as a counter reaction of the reduction reaction. The main oxidation reaction is a reaction in which the material constituting the sheath is ionized and eluted. By this oxidation reaction, Fe ₃ O ₄ or Fe ₂ O ₃ is generated in the sheath, and eventually an oxide film is formed on the sheath surface. As described above, since the oxidant is generated by radiolysis of the cooling water, the cooling water has a low oxygen concentration in the gap where the volume of the cooling water is small. Therefore, the oxide film grows on the inner surface of the sheath facing the gap. Is disturbed. On the other hand, the oxide film grows at other portions and the thickness of the oxide film becomes thicker. Therefore, ionization and elution of the sheath base material easily occur in the gap. As a result, oxygen concentration cells are formed inside and outside the gap, and the portion of the sheath that faces the gap is fixed to the anode, and the other portion is fixed to the cathode to form a macrocell that undergoes corrosion. Corrosion in which the sheath base material elutes may occur on the inner surface of the sheath. In this way, a form of corrosion in which the anode and the cathode are separated and only a specific part is selectively corroded is called “macrocell corrosion”.

  To summarize the above explanation, immediately after the start of the reactor, since the oxide film is not formed on the entire surface of the sheath of the reactor control rod, the sheath takes the form of full corrosion, but during the rated operation of the reactor Then, an oxide film is generated at a location where oxidizing species such as oxygen and hydrogen peroxide generated by the above-described radiolysis of the cooling water are present. For this reason, when the rated operation of the reactor is continued, an oxide film is formed on the sheath surface of the reactor control rod, but the cooling water flows in the gap formed between the hafnium (neutron absorbing member) and the sheath. In the case where a portion where the stagnation is significantly generated occurs, there is a possibility that the thickness of the oxide film differs between the inner surface of the sheath facing the gap and the other portion. For this reason, crevice corrosion which selectively elutes only by the sheath inner surface facing a crevice with a thin oxide film may arise.

  Japanese Patent Application Laid-Open No. 2010-54394 discloses a technique for suppressing crevice corrosion occurring on the inner surface of the sheath facing the gap formed in the nuclear reactor control rod. In this nuclear reactor control rod, the gap formed between the inner surface of the sheath and the hafnium member, which is a neutron absorbing member disposed in the sheath, is set within a range of 0.2 mm to 1.0 mm.

  Further, as described in, for example, JP 2009-186346 A, JP 2010-216881 A, and JP 2010-164508 A, a corrosion-resistant film is formed on the surface of the structural member of the reactor control rod. Methods are also being considered. JP 2009-186346 A describes that an oxide film is formed on the inner surface of the sheath facing the hafnium elliptic tube. Japanese Patent Application Laid-Open No. 2010-216881 describes that one or both surfaces of a hafnium member disposed in a sheath are coated with zirconium or a zirconium alloy. JP 2010-164508 discloses Cr, Zn, Zr, Ti and Hf on the inner surface of the sheath facing the hafnium elliptic tube in order to prevent crevice corrosion in the reactor control rod sheath (stainless steel). The formation of any one of the films is described.

JP-A-2006-38483 and JP-A-2006-38483 disclose a method for suppressing the attachment of radionuclides to the inner surface of a pipe by forming a ferrite film on the inner surface of a stainless steel pipe communicated with a reactor pressure vessel of a nuclear power plant. It is proposed in 2007-192745. Furthermore, Japanese Patent Laid-Open No. 2001-91688 discloses zinc chromite (ZnCr ₂ O ₄ ) and chromium oxide on the surface of the constituent member that contacts the cooling water in order to suppress stress corrosion cracking of the constituent member of the nuclear power plant. It describes that a composite oxide layer of zinc and chromium in which (Cr ₂ O ₃ ) is mixed is formed. Japanese Patent Laid-Open No. 2000-352597 describes stabilizing Cr contained in a component of a nuclear power plant. This stabilization of Cr alleviates the stress corrosion cracking susceptibility of the component, We are trying to suppress corrosion. The suppression of corrosion can reduce the exposure dose during periodic inspection. The stabilization of Cr proposes to form a compound in the form of MCr ₂ O ₄ (M is a mixture of one or more of Zn, Ni, Fe and Co) on the surface of the component. . As a method for forming MCr ₂ O ₄ , for example, FeCr ₂ O _{4 on} the surface of the constituent member, one or more of surface treatments of plating, painting, lining, thermal spraying, plating, prefilming, and polishing are used.

Japanese Patent Laid-Open No. 2-10299 JP 2002-71868 A JP-A-9-61576 JP 2002-71868 A JP 2010-54394 A JP 2010-216881 A JP 2009-186346 A JP 2010-164508 A JP 2006-38483 A JP 2007-192745 A JP 2001-91688 A JP 2000-352597 A

Computer Calculated Potential pH Diagrams to 300 ℃ Volume2: Handbook of Diagrams, Electric Power Research Institute, (1983)

  In the nuclear reactor control rod that is placed in the reactor and taken into and out of the core, tensile and compressive stresses are repeatedly applied to the blades in order to repeat the vertical movement, and the hafnium in the sheath during reactor startup The surface temperature of the elliptic tube varies from room temperature to 300 ° C. or higher. Furthermore, the reactor control rod is irradiated with radiation. For this reason, for example, as described in JP 2009-186346 A and JP 2010-164508 A, when a coating is formed on the inner surface of the sheath, generation of cracks in the coating, and this There is concern about peeling of the film from the sheath.

  When cracks etc. occur in the film formed on the sheath inner surface, the sheath base material is exposed at the position where cracks etc. occur in the film, so that corrosion tends to occur in the base material at that position, Due to the superiority and inferiority of the electrochemical characteristics of the film and the base material, there is a possibility of further accelerating the dissolution of the base material compared to the case where no film is applied. Further, when a corrosion-resistant metal such as zirconium is used for the sheath itself, since zirconium has a density higher than that of stainless steel, there is a concern that the weight of the entire nuclear reactor control rod increases and the equipment specifications are not satisfied.

  An object of the present invention is to provide a nuclear reactor control rod that can further suppress crevice corrosion of a sheath.

The features of the present invention that achieve the above-described object are as follows. Four sheaths extending from the tie rods extending in four directions, which are attached to the handle, the lower support member, and the tie rod and have a U-shaped cross section, and the respective sheaths. comprising arranged a neutron absorbing member, the metal chromium layer is formed on the inner surface of the sheath, faces the neutron absorbing member Cr ₂ O ₃ layer is formed on the surface of the metallic chromium layer, the reactor When loaded in the pressure vessel, a metal chromium layer and a Cr ₂ O ₃ layer are formed .

Since Cr ₂ O ₃ layer and a metal chromium layer between the sheath is formed, even if some peeling of the Cr ₂ O ₃ layer to be or Cr ₂ O ₃ layer with formation of cracks, a metal chromium layer As a result, the sheath is not exposed to cooling water, and the crevice corrosion of the sheath can be further suppressed.

  According to the present invention, according to the present invention, crevice corrosion of the sheath can be further suppressed in the nuclear reactor control rod.

BRIEF DESCRIPTION OF THE DRAWINGS It is a block diagram of the nuclear reactor control rod of Example 1 which is one suitable Example of this invention. It is II-II sectional drawing of FIG. FIG. 3 is an enlarged view of a part III in FIG. 2. 2 is a flowchart of a manufacturing process of the reactor control rod according to the first embodiment. It is explanatory drawing explaining Cr layer formation to the sheath inner surface of the reactor control rod in the Cr layer formation process shown in FIG. It is an explanatory view for explaining the formation of _Cr 2 _{O 3} layer to the inner surface of the sheath of the reactor control rods in _Cr 2 _{O 3} layer forming step shown in FIG. 4, (A) is used in the formation of the _Cr 2 _{O 3} layer configuration and explanatory diagram showing the formation of a _Cr 2 _{O 3} layer using the _Cr 2 _{O 3} layer forming apparatus of _Cr 2 _{O 3} layer forming apparatus for, (B) is a sheath of circular nozzles of _Cr 2 _{O 3} layer forming apparatus It is explanatory drawing which shows the state inserted between inner surfaces. FIG. 5 is a process diagram of assembling the reactor control rod shown in FIG. 4. It is explanatory drawing which shows the influence on the anode polarization curve of the stainless steel immersed in the deaeration pure water of the element contained in stainless steel. It is an explanatory view for explaining the formation of Cr ₂ O ₃ layer to the inner surface of the sheath of is another embodiment example 2 of reactor control rods of the present invention, (A) for the formation of the Cr ₂ O ₃ layer configuration and explanatory diagram showing the formation of a _Cr 2 _{O 3} layer using the _Cr 2 _{O 3} layer forming apparatus other _Cr 2 _{O 3} layer forming apparatus used, (B) other _Cr 2 _{O 3} layer forming apparatus It is explanatory drawing which shows the state which inserted this annular nozzle between the inner surfaces of a sheath.

  The inventors have cracked or formed a film (an oxide film or a film such as Cr) formed on the inner surface of the sheath described in JP2009-186346A and JP2010-164508A. A study was conducted on measures to prevent corrosion of the base material of the sheath even when the sheath was peeled off from the inner surface of the sheath.

An experiment conducted by the inventors upon the examination will be described. The corrosion reaction of the metal member immersed in the aqueous solution is transfer of electric charge between the metal member and a component contained in the aqueous solution. Corrosion is an event in which the metal M contained in the metal member becomes metal ions M ^{n +} and elutes into the liquid phase in contact with the metal member according to the equation (1).

M → M ^{n +} + ne ⁻ (1)
Therefore, the magnitude of the corrosion rate of the metal member can be determined by evaluating the amount of charge exchanged at the solid-liquid interface on the surface of the metal member as current. Therefore, the influence of the elements constituting the metal member on the ease of charge transfer with water on the surface of the metal member immersed in pure water simulating the temperature in the boiling water reactor is examined. did. Specifically, each test piece of SUS304 stainless steel and SUS316L stainless steel is immersed in pure water not containing an oxidizing agent at a temperature simulating the inside of a boiling water reactor (BWR), and these test pieces are immersed. The anodic polarization curve was measured. Furthermore, in order to investigate the governing factors of the corrosion characteristics of these stainless steels, the respective anodic polarization curves of Fe, Ni and Cr, which are elements constituting each stainless steel, were measured and compared with the corrosion characteristics of each stainless steel.

The experiment for measuring the anodic polarization curve was performed under conditions that simulated the in-furnace environment of the BWR. That is, using pure water having a conductivity of 0.1 μS · cm ⁻¹ or less, pressurizing the pure water to 8 MPa in order to prevent boiling, maintaining the temperature of the pure water at 280 ° C. Guided into the housed hot bath. As test specimens, commercially available SUS304 stainless steel, SUS316L stainless steel, pure Fe, pure Ni, and pure Cr were used separately, and each test specimen was purified under the above conditions in a high-temperature bath. Soaked in water. Each of the above five types of test pieces of different materials was prepared, and the experiment was performed under the above conditions. The anodic polarization curve was measured by applying a potential to each test piece immersed in pure water using a potentiostat and measuring the current at that time.

FIG. 8 shows the anodic polarization curves of SUS304 stainless steel, SUS316L stainless steel, pure Fe, pure Ni, and pure Cr, which are measurement results of the anodic polarization curve. FIG. 8 shows each of Fe, Ni, and Cr in pure water at 573 K and pH 5.6 described in Computer Calculated Potential pH Diagrams to 300 ° C. Volume 2: Handbook of Diagrams, Electric Power Research Institute, (1983). The changes in the morphology of the stable chemical species depending on the corrosion potential are also shown. According to Computer Calculated Potential pH Diagrams to 300 ° C. Volume 2: Handbook of Diagrams, Electric Power Research Institute, (1983), Fe depends on the corrosion potential of metal members, and Fe is Fe ₃ O ₄ , Fe ₂ O ₃ and FeO _4. ² changes to Cr, Cr changes to Cr ₂ O ₃ , Cr (OH) ₃ and Cr ₂ O ₇ ^2−, and Ni changes to NiO and Ni ₃ O ₄ .

  The current density of the anodic polarization curve (vertical axis in FIG. 8) is the amount of metal ionized from the surface of the test piece per unit time / unit area and eluted into the liquid phase per unit time / unit area according to the equation (1), ie, metal per unit area The elution rate is shown. Since the corrosion potential on the horizontal axis in FIG. 8 is an index of the corrosion environment strength, the potential dependence of the elution rate of each metal shown in FIG. 8 represents a characteristic that correlates the corrosion environment strength and the corrosion characteristics of the test piece. Yes.

As a result of comparison, the corrosion characteristics of the two types of stainless steel shown in FIG. 8 are mainly due to the elution behavior of Cr, and −0.4 Vvs. It was found that the peak due to Fe was superimposed only in the vicinity of SHE. The elution behavior of Cr is about -0.1 Vvs. It changes at the boundary of SHE, and is -0.1 Vvs. Above SHE, the dissolution rate is increased by overpassive dissolution, but at -0.1 Vvs. Below SHE, Cr ₂ O ₃ is stable, so the elution rate is lowered.

  As described above, oxygen and hydrogen peroxide are not easily generated in the gap formed in the reactor control rod, and a reduction reaction occurs in the process in which the oxidant generated in the bulk diffuses into the gap. Therefore, the gap is in a low oxidizing species concentration state. Therefore, it is considered that the portion of the stainless steel sheath facing the gap is at a low potential close to the natural immersion potential (about −0.5 V vs. SHE) in FIG. On the other hand, the potential at the portion of the stainless steel sheath that does not face the gap is considered to be higher than the portion of the stainless steel sheath that does not face the gap. This is because the respective concentrations of oxygen and hydrogen peroxide contained in the cooling water that contacts the portion of the stainless steel sheath that does not face the gap (for example, the outer surface of the sheath) flow through the gap, It is because it is higher than each density | concentration of oxygen and hydrogen peroxide contained in the cooling water which contacts the site | part (sheath inner surface) which faces the clearance gap of steel sheaths. Therefore, a portion of the stainless steel sheath facing the gap is in an active state, and macrocell corrosion occurs where corrosion proceeds selectively at this portion.

The width of the gap decreases due to thermal expansion of the hafnium member arranged in the sheath of the reactor control rod, and the concentration of oxygen and hydrogen peroxide in the cooling water in the gap decreases, and the corrosion potential on the sheath inner surface is reduced. -0.4 V vs. When lowered to the vicinity of SHE, when the oxide film is not formed on the inner surface of the stainless steel sheath, the inner surface of the sheath becomes active, and the corrosion rate of the inner surface of the sheath shows a high value due to Fe elution. On the other hand, -0.4Vvs. The original Cr elution characteristics in the vicinity of SHE are characteristics in a corrosion potential region where Cr ₂ O ₃ can stably exist. From the above, since the oxidation is difficult to proceed at the portion of the stainless steel sheath facing the gap, it is invented that it is difficult to form a Cr oxide that can be stably present, which is the cause of macrocell corrosion. They thought.

Although the current density of the stainless steel in the active state is about 5 .mu.A · ^{cm -2,} the current density of Cr in the same potential range is 0.2 .mu.A · ^{cm -2,} very 1/25 of the current density stainless steel The value becomes low. For this reason, the inventors previously formed a Cr ₂ O ₃ coating on the inner surface of the sheath facing the neutron absorbing member (for example, hafnium member) before the reactor control rod is installed in the reactor pressure vessel. As a result, even if a gap environment is formed in which the concentrations of oxygen and hydrogen peroxide in the cooling water in the gap are reduced, −0.4 Vvs. The current density of the inner surface of the sheath in the active state of the SHE vicinity is reduced from 5 .mu.A · ^{cm -2} to 0.2 .mu.A · ^{cm -2} to about 1/25, also found that can reduce corrosion rate inevitably inner surface of the sheath. Furthermore, due to the characteristics of pure Cr, -0.4 Vvs. Because of the _Cr 2 _{O 3} is stable in the SHE vicinity of potential, than _Cr 2 _{O 3} layer by providing the Cr layer on the base material side, if _{the Cr} 2 _{O 3} layer is lost by mechanical causes, etc. However, by forming the Cr layer between the Cr ₂ O ₃ layer and the sheath, the lost part of the Cr ₂ O ₃ layer can be recovered, and the corrosion resistance of the sheath can be ensured for a longer period of time. The inventors have found that this is possible.

Based on the above examination, the inventors previously formed a Cr layer on the inner surface of the sheath facing the neutron absorbing member disposed in the sheath at the time of manufacturing the reactor control rod, and further formed the Cr layer. by forming the Cr ₂ O ₃ layer on the surface of, it led I to form a composite film containing a Cr ₂ O ₃ layer on the Cr layer and the Cr layer on the inner surface of the sheath. In this configuration, (a) the formation of the Cr ₂ O ₃ layer on the liquid contact surface of the sheath is a metal per unit time from the inner surface of the sheath to the cooling water flowing through the gap formed between the neutron absorbing member and the inner surface of the sheath. Elution amount, that is, the corrosion rate of the sheath is reduced, and (b) the formation of the metal Cr layer between the Cr ₂ O ₃ layer and the sheath may cause the outer Cr ₂ O ₃ layer to dissolve, peel, or otherwise Even in the case of loss due to the above reason, the Cr ₂ O ₃ layer is recovered by using Cr of the Cr layer on the surface of the Cr layer formed on the inner surface of the sheath. For this reason, the corrosion resistance of the sheath can be maintained, and crevice corrosion can be suppressed and the corrosion rate can be reduced.

  Examples of the present invention reflecting the above examination results will be described below.

  A reactor control rod according to embodiment 1, which is a preferred embodiment of the present invention, will be described with reference to FIGS. 1, 2, and 3. FIG. The reactor control rod 1 of the present embodiment is a control rod used for a boiling water reactor (BWR).

  The nuclear reactor control rod 1 has a cross shape in cross section, and a tie rod 7 is disposed on the axis, and has four blades 2 extending from the tie rod 7 in all directions. The handle 5 is attached to the upper end portion of the tie rod 7, and the lower support member 8 is attached to the lower end portion of the tie rod 7. The lower support member 8 is a lower support plate (or a drop speed limiter). A plurality of rollers 4 are rotatably attached to the lower support member 8. These rollers 4 are in contact with the outer surface of the channel box of the fuel assembly loaded in the core, and have a function of smoothly moving the reactor control rod 1 between the fuel assemblies.

  Each blade 2 has a sheath 6 made of stainless steel (SUS304, SUS316L, etc.) having a U-shaped cross section, and hafnium members 3U, 3L which are flat tubes, for example, elliptical tubes (see FIG. 1). ). The upper end of the sheath 6 is welded to the handle 5, and the lower end of the sheath 6 is welded to the lower support member 8. A plurality of tabs (projections) 13 are formed at predetermined intervals in the axial direction at both ends of the U-shape of the sheath 6. These tabs 13 are parts of the sheath 6 but are protruding toward the tie rod 7 side. These tabs 13 are joined to the side surface of the tie rod 7 by welding. The above-described joining of the sheath 6, the tie rod 7, the handle 5, and the lower support plate 8 is performed by, for example, laser welding.

  Two hafnium members 3U and two hafnium members 3L are arranged in the axial direction of the reactor control rod 1 in a space formed in the sheath 6 of one blade 2. The hafnium member 3U is located above the hafnium member 3L, and the axial lengths of the hafnium members 3U and 3L are the same. The hafnium member 3U is attached to a tongue-like portion 10U formed at the lower end portion of the handle 5 with a pin 11U. The hafnium member 3L is attached to a tongue-like portion 10L formed at the upper end portion of the lower support member 8 with a pin 11L. Thus, the hafnium member 3U has an upper end attached to the handle 5 and a hafnium member 3L attached to the lower support plate 8. These hafnium members are neutron absorbing members. A gap (not shown) is formed between the lower end of the hafnium member 3U and the upper end of the hafnium member 3L so that the hafnium members 3U and 3L do not come into contact with each other even if the hafnium members 3U and 3L are thermally expanded during the operation of the BWR. Has been.

  In the cross section of one blade 2 (II-II cross section in FIG. 1), the two hafnium members 3U are arranged in parallel with each other in the sheath 6 and in parallel with the tie rod 4 (see FIG. 2). Similarly to the hafnium member 3U, the two hafnium members 3L are also arranged in parallel with each other in the sheath 6 and arranged in parallel with the tie rod 4.

A Cr layer (Cr coating) 14 is formed on the inner surface of the sheath 6 so as to cover the inner surface of the sheath 6. A Cr ₂ O ₃ layer (Cr ₂ O ₃ coating) 15 is formed on the surface of the Cr layer 14 so as to cover the surface of the Cr layer 14. On the inner surface of the sheath 6, a Cr layer 14 and a Cr ₂ O ₃ layer 15 are formed in this order toward the hafnium members 3U and 3L. The Cr ₂ O ₃ layer 15 is substantially opposed to the hafnium members 3U and 3L. A gap 16 through which cooling water flows is formed between the inner surface of the sheath 6, specifically, between the Cr ₂ O ₃ layer 15 and the hafnium members 3U and 3L (see FIG. 3).

  A plurality of openings 9 </ b> U are formed in the upper part of the sheath 6, and a plurality of openings 9 </ b> L are formed in the lower part of the sheath 6. A plurality of openings 12U are formed in each hafnium member 3U, and a plurality of openings 12L are formed in each hafnium member 3L.

  A method for manufacturing the reactor control rod 1 having the sheath 6 on which the Cr coating 6a and the Cr diffusion layer are formed will be described with reference to FIG. A Cr film and a Cr diffusion layer are formed on the surface of the sheath member by surface treatment (step 1). A Cr coating 6a is formed on one surface (one surface) of a stainless steel plate-like sheath member 6b which is a base material of the sheath 6. The Cr film 6a is a film containing a metal that promotes passivation of stainless steel. Formation of the Cr film 6a on one side of the sheath member 6b is performed as follows.

  A method for manufacturing the reactor control rod 1 of the present embodiment will be described with reference to FIGS. 4, 5, 6, and 7.

  First, the sheath is processed (step S1). A plurality of openings 9U and 9L are processed in a stainless steel plate which is a material of the sheath 6, and then the stainless steel is bent into a U shape to manufacture the sheath 6. An activation process is performed on the surface of the sheath (step S2). The activation treatment on the surface of the sheath 6 is a treatment for removing the passive film formed on the surface of the sheath 6. The passive film formed on the surface of the sheath 6 is removed using, for example, an oxalic acid aqueous solution and a potassium permanganate aqueous solution. First, an aqueous oxalic acid solution is brought into contact with the surface of the sheath 6 on which the passive film is formed, and then an aqueous potassium permanganate solution is brought into contact with the surface to remove the passive film. The sheath is washed (step S3), and the sheath is dried (step S4). The surface of the sheath 6 from which the passive film has been removed is washed with pure water. Air is blown onto the surface of the washed sheath 6 to dry the sheath 6. The air to be blown may be warm air.

  A Cr layer is formed on the sheath surface (step S5). A Cr layer (Cr coating) 14 is formed on the inner surface of the dried sheath 6 (see FIG. 4). Formation of the Cr layer (metal CR layer) 14 on the inner surface of the sheath 6 is performed using a Cr layer forming apparatus 20 shown in FIG. The Cr layer forming apparatus 20 includes an electrolytic cell 21, an electrode 22, a power source 23 and a wiring 24. The electrode 22 is connected to the power source 23 by a wiring 24 </ b> A, and the other wiring 24 </ b> B is also connected to the power source 23.

The sheath 6 bent in a U shape is immersed in a Cr plating solution 25 filled in the electrolytic cell 21. The electrode 22 connected to the power source 23 by the wiring 24A is disposed between the bent side walls of the sheath 6, and the wiring 24A connected to the power source 23 is connected to the bent portion of the sheath 6. In this state, a current is supplied from the power source 23 to the electrode 22 through the wiring 24. This current flows toward the sheath 6 through the Cr plating solution 25 existing in the gap 6A between the bent side walls of the electrode 22 and the sheath 6, and returns to the power source 23 through the wiring 24B. By supplying electric current, Cr contained in the Cr plating solution 25 adheres to the inner surface of the sheath 6, and a Cr layer 14 covering the inner surface of the sheath 6 is formed on the inner surface of the sheath 6. The value of the current supplied to the electrode 22 and the supply time of the current that can form the Cr layer 14 having a desired thickness (for example, 20 μm) uniformly on the inner surface of the sheath 6 are obtained in advance by experiments, When the Cr layer 14 is formed on the inner surface, a current having the current value is supplied to the electrode 22 during the supply time. Considering that the Cr ₂ O ₃ layer 15 is generated in Step S8 using Cr existing on the surface portion of the Cr layer 14 formed in Step S5, the Cr layer 14 formed on the inner surface of the sheath 6 in Step S5 The thickness is made larger than the actually required thickness of the Cr layer 14 (for example, 10 μm).

  In this embodiment, the Cr layer is formed on the inner surface of the sheath 6 by electrolytic plating, but instead of electrolytic plating, any one of electroless plating, physical vapor deposition, chemical vapor deposition, thermal spraying, and cold spraying is used. Thus, a Cr layer may be formed on the inner surface of the sheath 6.

  After the formation of the Cr layer, the sheath is washed similarly to step S3 (step S6), and the sheath is dried similarly to step S4 (step S7).

A Cr ₂ O ₃ layer is formed (step S8). After the drying of the sheath 6 in step S7 is completed, a Cr ₂ O ₃ layer (Cr ₂ O ₃ coating) 15 is formed on the surface of the Cr layer 14 formed on the inner surface of the sheath 6. The Cr ₂ O ₃ layer 15 is formed using a chromium oxide layer forming apparatus 30 shown in FIG.

  The chromium oxide layer forming apparatus 30 includes a tubular nozzle 31, a guide rail 33, a traveling device 34, a heating device 35, and a gas cylinder 36, as shown in FIGS. The traveling device 34 is movable along the guide rail 33. A stainless steel tubular nozzle 31 in which a plurality of ejection holes 32 are formed is attached to the traveling device 34 and extends downward. A flexible fluid transfer pipe 37 connected to the tubular nozzle 24 is connected to a gas cylinder 36 in which pressurized air is stored. A heating device 35 is provided in the fluid transport pipe 29. The outer diameter of the tubular nozzle 31 is smaller than the width between the opposing inner surfaces of the U-shaped sheath 6.

  The sheath 6 with the Cr layer 14 formed on the inner surface is attached to a holding device (not shown) so that the U-shaped end is downward. The guide rail 33 is attached to a support device (not shown) and is located above the open end of the sheath 6. The open end of the guide rail 33 and the sheath 6 are arranged in parallel. A tubular nozzle 31 attached to the traveling device 34 is inserted between the opposed inner surfaces of the sheath 6 from the open end (see FIG. 6B). Each ejection hole 32 formed in the tubular nozzle 31 faces the normal direction of the inner surface of the sheath 6. The tubular nozzle 31 moves in the sheath 6 from one end in the longitudinal direction of the sheath 6 toward the other end by moving the traveling device 34 along the guide rail 33.

When the formation of the Cr ₂ O ₃ layer 15 on the surface of the Cr layer 14 formed on the inner surface of the sheath 6 is started, the tubular nozzle 31 is positioned at one end in the longitudinal direction of the sheath 6. The pressurized air in the gas cylinder 36 is supplied to the heating device 35 through the fluid transport pipe 29 by opening a valve (not shown) provided in the gas cylinder 36. Air heated to a temperature in the range of 100 ° C. to 300 ° C., for example, 300 ° C., by the heating device 35 is supplied into the tubular nozzle 31 by the fluid conveyance pipe 37. The air is ejected from the plurality of ejection holes 32 toward the inner surface of the sheath 6, and the Cr ₂ O ₃ layer 15 is oxidized by oxidizing Cr contained in the Cr layer 14 on the surface of the Cr layer 14 formed on the inner surface of the sheath 6. The heat and oxygen necessary to form the are supplied. When the heated air is ejected from the plurality of ejection holes 32, the Cr in the surface portion that is a part of the Cr layer 14 is oxidized, and the Cr ₂ O ₃ layer 15 covering the surface of the Cr layer 14 becomes the Cr layer 14. Formed on the surface. Other gas may be used as long as it is a gas heated to a temperature within the range of from 0 to 300 ° C. containing 20% or more oxygen instead of air.

The tubular nozzle 31 that ejects the heated air is moved at a predetermined speed from one end of the sheath 6 to the other end thereof in the longitudinal direction of the sheath 6 by a traveling device 34 that travels along the guide rail 33. Is done. A Cr ₂ O ₃ layer 15 having a predetermined thickness (for example, 10 μm) is formed on the surface of the Cr layer 14 formed on the sheath 6 by heated air ejected from the plurality of ejection holes 32. When the tubular nozzle 31 reaches the other end of the sheath 6, the ejection of the heated air from the tubular nozzle 31 is stopped, and the movement of the tubular nozzle 31 is also stopped. As a result, the generation of the Cr ₂ O ₃ layer 15 is completed, and the Cr ₂ O ₃ layer 15 having a thickness of 10 μm is formed on the surface of the Cr layer 14 formed on the inner surface of the sheath 6 over the entire length in the longitudinal direction of the sheath 6. Formed.

Of the Cr contained in the Cr layer 14 generated in step S5, Cr present in the region of 10 μm thickness from the surface of the Cr layer 14 toward the sheath 6 is oxidized in step S8 to become the Cr ₂ O ₃ layer 15. , at the time when the product is finished the _Cr 2 _{O 3} layer 15, Cr layer 14 having a thickness of 10μm is formed on the inner surface of the sheath 6, _Cr 2 _{O 3} layer 15 having a thickness of 10μm is formed on the surface of the Cr layer 14 .

The correlation between the thickness of the Cr ₂ O ₃ layer 15 formed with the moving speed of the traveling device 34 is measured in advance, by controlling the moving speed of the traveling device 34 on the basis of this correlation, Cr ₂ O The thickness of the _three layers 15 is adjusted within a range of 10 μm or less. While the Cr ₂ O ₃ layer 15 is being formed, the temperature of the air supplied from the heating device 35 to the tubular nozzle 31 and the temperature of the inner surface of the sheath 6 against which the air hits the temperature measuring device such as a thermocouple. Monitored by measurement by When the temperature of the steam supplied to the tubular nozzle 31 deviates from the set temperature, the heating amount by the heating device 35 is controlled.

The formation of the Cr ₂ O ₃ layer 15 by oxidation of Cr existing on the surface portion which is a part of the Cr layer 14 is as follows: (A) Water vapor having a temperature in the range of 100 ° C. to 300 ° C. is formed on the inner surface of the sheath 6. Steam oxidation that oxidizes Cr present on the surface portion of the Cr layer 14 by spraying on the formed Cr layer 14, (B) pure water having a temperature in the range of 100 ° C. to 300 ° C. was formed on the inner surface of the sheath 6. The Cr layer 14 formed on the inner surface of the sheath 6 by high-temperature hydroxylation that sprays the Cr layer 14 to oxidize Cr present on the surface of the Cr layer 14 and (C) a liquid oxidizing agent at room temperature (for example, 15 ° C.). Chemical oxidation that oxidizes Cr present on the surface portion of the Cr layer 14 by spraying on the surface of the sheath 6, and (D) a conductive aqueous solution (for example, 100 mMol · kg ⁻¹ sodium sulfate aqueous solution) at room temperature (for example, 15 ° C.) Cr formed on the inner surface Electrochemical oxidation in which an electric field is applied to the solid-liquid interface on the inner surface of the sheath 6 by being brought into contact with the layer 14 to oxidize Cr existing on the surface portion of the Cr layer 14, and (E) the sheath 6 having the Cr layer 14 formed on the inner surface. And (F) physical oxidation that oxidizes Cr present on the surface of the Cr layer 14 by bringing the heater into contact with the Cr layer 14 formed on the inner surface of the sheath 6. You may carry out by either.

A nuclear reactor control rod is assembled (step S9). After the formation of the Cr ₂ O ₃ layer 15 on the inner surface of the sheath 6 is finished, the assembly of the reactor control rod 1 is started. The assembly of the reactor control rod 1 will be described with reference to FIG.

The manufacture of the control rod 1 will be briefly described with reference to FIG. A hafnium member 3U is attached to the tongue 10U of the handle 5 with a pin 11U. The handle 5 is joined to one end of the tie rod 7. The hafnium member 3L is attached to the tongue-like portion 10L of the lower support member 8 to which the roller 4 and the connector 17 are attached by pins 11L. The lower support member 8 is joined to the other end of the tie rod 7. The sheath 6 in which the Cr layer 14 is formed on the inner surface in step S5 and the Cr ₂ O ₃ layer 15 is formed on the surface of the Cr layer 14 in step S8 is welded to the handle 5, the tie rod 7 and the lower support member 8 by laser welding. Be joined. Hafnium members 3U and 3L are disposed between the opposing inner surfaces of the sheath 6 and face the Cr ₂ O ₃ layer 15 formed on the sheath 6. In this way, the reactor control rod 1 is manufactured.

  The manufactured reactor control rod 1 is loaded into the reactor pressure vessel of the boiling water reactor (step S10). Step S10 is only described in FIG. 4 in order to clarify the loading timing of the reactor control rod 1 into the reactor pressure vessel, and is not included in the manufacturing process of the reactor control rod 1.

  The reactor control rod 1 loaded in the reactor pressure vessel is connected to a control rod drive mechanism (not shown) provided at the bottom of the reactor pressure vessel by a connector 17 provided at the lower end of the lower support member 8. Connected. The reactor control rod 1 is taken in and out by a control rod drive mechanism in a core loaded with a plurality of fuel assemblies in order to control the reactor power. The control rod drive mechanism performs an operation of inserting the reactor control rod 1 into the core and an operation of extracting the control rod 1 from the core.

Reactor water (cooling water) flowing in the reactor pressure vessel flows into the sheath 6 from the opening 9L formed in the sheath 6, cools the hafnium members 3U, 3L, and out of the sheath 6 from the other opening 9U. leak. Part of the reactor water that has flowed into the sheath 6 flows into the hafnium member 3U through the small-diameter opening 12U provided in the hafnium member 3U, and also passes through the small-diameter opening 11 formed in the hafnium member 3L. Flows into the hafnium member 3L. Thus, the reactor water flows into the hafnium members 3U and 3L, whereby the cooling effect of these hafnium members is increased. Some of the reactor water that has flowed into the sheath 6 is formed between the hafnium members 3U and 3L and the inner surface of the sheath 6, specifically, Cr ₂ O formed on the hafnium members 3U and 3L and the sheath 6. _It rises in contact with the Cr ₂ O ₃ layer 15 in the gap formed between the _three layers 15 (see FIG. 4).

The nuclear reactor control rod 1 of the present embodiment forms a composite film containing Cr of the Cr layer 14 and the Cr ₂ O ₃ layer 15 on the inner surface of the sheath 6 that forms a gap between the hafnium members 3U and 3L. ing. That is, the composite film containing Cr of the Cr layer 14 and the Cr ₂ O ₃ layer 15 is formed over the entire inner surface of the sheath 6 facing the gap. A Cr layer 14 is formed on the inner surface of the sheath 6, and a Cr ₂ O ₃ layer 15 is formed on the surface of the Cr layer 14. Since each of the Cr layer 14 and the Cr ₂ O ₃ layer 15 has an anticorrosive effect, charge transfer between the sheath 6 and the reactor water flowing through the gap can be suppressed. Generation of crevice corrosion can be prevented.

In particular, the nuclear reactor control rod 1 in which the Cr layer 14 and the Cr ₂ O ₃ layer 15 are formed on the inner surface of the sheath 6 flows in the gap 16 formed between the hafnium members 3U and 3L and the sheath 6. Macrocell corrosion that occurs in the sheath 6 due to the formation of the oxygen concentration cell on the sheath 6 due to the lower concentration of oxidizing species (oxygen, hydrogen peroxide, etc.) contained in the reactor water, Since crevice corrosion can be further suppressed, the life of the reactor control rod 1 can be extended.

Further, when the reactor control rod 1 is arranged in the reactor pressure vessel, the Cr ₂ O ₃ layer 15 is cracked for some reason or a part of the Cr ₂ O ₃ layer 15 is peeled off. Cr in, even reactor water flowing in said gap intrudes to the release portion of the crack or Cr ₂ O ₃ layer 15 of Cr ₂ O ₃ layer 15, the reactor water, which covers the inner surface of the sheath 6 It only contacts the layer 14 and does not directly contact the inner surface of the sheath 6. Therefore, formation of cracks in the _Cr 2 _{O 3} layer 15, or even when a part of _Cr 2 _{O 3} layer 15 is peeled off, it is possible to prevent the occurrence of crevice corrosion in the sheath 6.

The peeling unit that occurred Cr ₂ O ₃ layer 15 crack or _Cr 2 _{O 3} layer 15 that occurred in the Cr layer 14 exposed to the reactor water, are exposed to reactor water at the surface of the Cr layer 14 Cr ₂ O ₃ is generated by the reaction of oxygen and hydrogen peroxide contained in the reactor water flowing through the gap formed between Cr of the Cr layer 14 and the hafnium members 3U and 3L and the inner surface of the sheath 6, The Cr ₂ O ₃ layer 15 is recovered on the surface of the Cr layer 14. Since the surface area of the Cr layer 14 exposed to the reactor water at the cracks or at the peeled portions is small, the action of oxygen and hydrogen peroxide in the reactor water containing a small amount of oxygen and hydrogen peroxide flowing in the gap causes A Cr ₂ O ₃ layer 15 is formed on the surface of the Cr layer 14 exposed to water. Therefore, the probability that crevice corrosion occurs in the sheath 6 is significantly reduced.

Since the Cr ₂ O ₃ layer 15 is generated by using the Cr on the surface part of the Cr layer 14 formed on the inner surface of the sheath 6, the adhesion between the Cr layer 14 and the Cr ₂ O ₃ layer 15 is excellent. ing.

Furthermore, since the Cr layer 14 is formed on the inner surface of the sheath 6 of the reactor control rod 1 by using the Cr layer forming apparatus 20, the Cr layer 14 that suppresses the occurrence of crevice corrosion is shortened on the inner surface of the sheath 6. Can be formed in time. Since the chromium oxide layer forming apparatus 30 is used to form the Cr ₂ O ₃ layer 15 on the surface of the Cr layer 14, the energy required for forming the Cr ₂ O ₃ layer 15 can be reduced by a simple apparatus that is easy to handle. Oxygen can be supplied, and Cr ₂ O ₃ 15 can be efficiently formed on the Cr layer 14 formed on the sheath 6.

  A reactor control rod according to embodiment 2, which is another embodiment of the present invention, will be described below. The reactor control rod of the present embodiment is also a control rod used in a boiling water reactor (BWR).

The reactor control rod of the present embodiment has the same configuration as the reactor control rod 1 of the first embodiment. The reactor control rod of the present embodiment is manufactured in the same process as the manufacturing process of the reactor control rod 1 of the first embodiment shown in FIGS. 4 and 7. In the manufacturing process of the reactor control rod of the present embodiment, the part different from the manufacturing process of the reactor control rod 1 is the generation process of the Cr ₂ O ₃ layer 15 in step S8. In the nuclear reactor control rod 1 of Example 1, the Cr ₂ O ₃ layer 15 was formed on the surface of the Cr layer 14 formed on the inner surface of the sheath 6 using the chromium oxide layer forming apparatus 30. In the furnace control rod, the Cr ₂ O ₃ layer 15 is formed on the surface of the Cr layer 14 formed on the inner surface of the sheath 6 by using the chromium oxide layer forming device 30A shown in FIG. 9 instead of the chromium oxide layer forming device 30. To do.

  The chromium oxide layer forming apparatus 30 </ b> A has a configuration in which the gas cylinder 36 is replaced with a tank 39 in the chromium oxide layer forming apparatus 30 and a pump 38 is provided in the fluid conveyance pipe 37. Other configurations of the chromium oxide layer forming apparatus 30A are the same as those of the chromium oxide layer forming apparatus 30. The fluid conveyance pipe 37 provided with the pump 38 is connected to the bottom of a tank 39 filled with water 40.

In step S8 in which the Cr ₂ O ₃ layer 15 is formed on the surface of the Cr layer 14 formed on the inner surface of the sheath 6, the chromium oxide layer forming apparatus 30A is used to form the Cr ₂ O ₃ layer 15. The formation of the Cr ₂ O ₃ layer 15 using the chromium oxide layer forming apparatus 30A will be described.

The sheath 6 with the Cr layer 14 formed on the inner surface is attached to a holding device (not shown) so that the U-shaped end is downward. The tubular nozzle 31 is inserted at one end of the sheath 6 between the opposing side surfaces of the sheath 6 bent into a U shape. The water 40 in the tank 39 is pressurized by the pump 38 and supplied to the heating device 35 through the fluid conveyance pipe 37. The heating device 35 heats the water 40 to 300 ° C. to make steam. This steam is discharged from the heating device 35 and supplied into the tubular nozzle 31 through the fluid transfer pipe 37. In order to form the Cr ₂ O ₃ layer 15 on the surface of the Cr layer 14 formed on the surface of the Cr layer 14 formed on the surface of the Cr layer 14 formed on the inner surface of the sheath 6 from the plurality of injection holes 32. Supply the necessary heat and oxygen. While the steam is ejected from the tubular nozzle 31, the traveling nozzle 34 moves the tubular nozzle 31 at a predetermined speed in the longitudinal direction of the sheath 6. A Cr ₂ O ₃ layer having a uniform thickness (for example, 10 μm) on the surface of the Cr layer 14 over the entire length in the longitudinal direction of the sheath 6 by the action of steam ejected from the plurality of ejection holes 25 as in the first embodiment. 15 is formed.

In step S9, the nuclear reactor control rod is assembled in the same manner as in Example 1 by using the sheath 6 in which the composite coating containing Cr of the Cr layer 14 and the Cr ₂ O ₃ layer 15 is formed on the inner surface. The manufactured reactor control rod of this embodiment is installed in the reactor pressure vessel and used for controlling the reactor power.

  The reactor control rod of the present embodiment can obtain each effect produced by the reactor control rod 1 of the first embodiment.

DESCRIPTION OF SYMBOLS 1 ... Reactor control rod, 2 ... Blade, 3U, 3L ... Hafnium member, 5 ... Handle, 6 ... Sheath, 7 ... Tie rod, 8 ... Lower support member, 13 ... Tab (protrusion part), 14 ... Cr layer, 15 ... _Cr 2 _{O 3} layer, 21: long nozzle, 22: 1-dimensional moving means, 23: rail, 24: fluid jetting hole, 20 ... Cr layer forming device, 21 ... electrolyzer, 22 ... electrode, 30, 30A ... Chrome oxide layer forming device, 31 ... tubular nozzle, 33 ... guide rail, 34 ... traveling device.

Claims (3)

A tie rod, a handle attached to the upper end of the tie rod, a lower support member attached to the lower end of the tie rod, an upper end attached to the handle, a lower end attached to the lower support member, and Four sheaths attached to the tie rod and having a U-shaped cross section extending in four directions from the tie rod, and a neutron absorbing member disposed in each sheath,
A metal chromium layer is formed on the inner surface of the sheath, a Cr ₂ O ₃ layer is formed on the surface of the metal chromium layer and faces the neutron absorbing member ;
The nuclear reactor control rod , wherein the metal chromium layer and the Cr ₂ O ₃ layer are formed when loaded into a reactor pressure vessel .   The nuclear reactor control rod according to claim 1, wherein the neutron absorbing member is a hafnium member. Wherein Cr ₂ reactor control rod according to claim 1 or 2 O ₃ layer is Cr ₂ O ₃ layer formed by oxidizing the surface of the metallic chromium layer.

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