EP3380787B1 - Générateur de vapeur, procédés de fabrication et utilisations correspondantes - Google Patents

Générateur de vapeur, procédés de fabrication et utilisations correspondantes Download PDF

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Publication number
EP3380787B1
EP3380787B1 EP15845497.5A EP15845497A EP3380787B1 EP 3380787 B1 EP3380787 B1 EP 3380787B1 EP 15845497 A EP15845497 A EP 15845497A EP 3380787 B1 EP3380787 B1 EP 3380787B1
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Prior art keywords
steam generator
dispo
content
metal layer
chromium
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EP15845497.5A
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German (de)
English (en)
French (fr)
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EP3380787A1 (fr
Inventor
Charles BRUSSIEUX
Michael Guillodo
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Areva NP SAS
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Framatome SA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B37/00—Component parts or details of steam boilers
    • F22B37/002—Component parts or details of steam boilers specially adapted for nuclear steam generators, e.g. maintenance, repairing or inspecting equipment not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B37/00—Component parts or details of steam boilers
    • F22B37/02—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler
    • F22B37/04—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler and characterised by material, e.g. use of special steel alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B22F2003/244—Leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2207/00—Aspects of the compositions, gradients
    • B22F2207/01—Composition gradients

Definitions

  • the invention generally relates to elements made of a metal alloy based on nickel, in particular the tubes of a nuclear reactor steam generator.
  • the documents US2002/155306 A1 and US2010/032061 A1 disclose a treatment method intended for nuclear reactor steam generator parts.
  • the primary liquid circulates inside the tubes and transfers its heat to the secondary liquid. It then passes inside the nuclear reactor core, where it heats up before being redirected to the steam generator. The plates are in contact with the primary liquid.
  • the internal surface of the tubes constitutes approximately 75% of the internal surface of the primary circuit in certain nuclear reactors.
  • the primary liquid also called primary medium
  • the primary medium is a solution whose main components are water, boric acid and lithine in order to obtain a pH close to temperature neutrality.
  • the temperature of the primary medium is close to 300°C (generally between 280 and 345°C).
  • the primary medium contains dissolved hydrogen.
  • the primary liquid is cold purified in a power plant chemistry circuit in order to limit its concentration of metal cations and colloids resulting from the corrosion of the materials in the circuit.
  • concentrations of metal cations in the primary media of power plants in operation are not known with precision but are close to the lowest published solubility limit concentrations.
  • the primary medium is the purest possible water containing traces of hydrogen and dissolved oxygen, and the temperature is around 290°C.
  • primary medium will be understood to mean any primary medium of a pressurized water reactor during the energy production phases, complying with the specifications of the main reactor operators or the main research and safety organizations in the field.
  • solubility of most of the compounds in a primary medium has been studied and is published in particular in the form of commercial databases such as those offered by the company OLI Systems.
  • the invention aims to propose a steam generator making it possible to limit the radioactive contamination of the primary circuit.
  • the tubes of the state of the art notably have a mass content of available chromium w Cr_dispo (p) of less than 0 over the first 200 nanometers of the surface metallic layer.
  • the invention relates to another method for manufacturing a steam generator having the above characteristics, which is an alternative to the above method, the method comprising a step of manufacturing the element by rolling an ingot with a non-carbon lubricant, or by continuous casting and then rolling with a non-carbon lubricant.
  • the invention relates to the use of a steam generator having the above characteristics in a pressurized water nuclear reactor, with the aim of limiting the oxidation liable to lead to the formation on the surface inside the element of filaments whose mass composition is rich in nickel, and/or the direct release into a primary liquid of ions or colloids from the zones where these filaments are likely to form, when the internal surface is exposed to the primary liquid during nominal operation of the pressurized water nuclear reactor.
  • the invention will be described below by detailing the constitution of an element 1 which is a steam generator tube.
  • the element may be a plate of the steam generator, a so-called internal side of which has an internal surface exposed to contact with the primary fluid.
  • Such an element is used in pressurized water nuclear reactor steam generators.
  • the primary liquid coming from the core circulates inside the tube or in contact with the plate.
  • Element 1 has, on an internal side intended to be exposed to the primary liquid, a surface metallic layer 7, having an internal surface 5 covered by an oxide layer 3.
  • oxide layer 3 typically has a thickness of less than 10 mm, due to the manufacturing method of element 1 described below.
  • This oxide layer typically comprises an oxide layer called the outer layer composed of spinel type oxides of iron, chromium and nickel, which covers another oxide layer called the inner oxide layer generally rich in chromium.
  • the thickness of the oxide layer 3 is defined as being the thickness measured by glow discharge spectroscopy (calibrated according to the state of the art) from the free external surface 4 until the mass content of oxygen is less than 50% of the mass content of oxygen at the free external surface 4.
  • the oxide layers can have a total thickness of up to a few micrometers.
  • the surface metallic layer 7 has a composition which differs from the composition of the nickel-based alloy, while remaining close to it. Under the superficial metal layer 7, there is the base metal 9 of the tube. Typically, layer 7 has a thickness of approximately 1 ⁇ m (see picture 2 ).
  • internal surface 5 of element 1 is therefore understood to mean the surface formed by the metal/internal oxide layer interface, delimiting the internal passage in which the primary liquid flows in the case of a tube.
  • the base metal 9 has substantially the mass contents of the alloy used to manufacture the tube.
  • the metallic surface layer 7 is mainly made of metal, and not of metallic oxide, although it contains non-metallic inclusions - inclusions that can be up to several hundred nanometers along their largest dimensions. It has mass contents which are slightly different from those of the base metal, resulting from the treatments applied during the manufacture of the tube.
  • the filaments 11 are torn from the oxide layer or dissolved during their growth and are drawn into the primary circuit. They thus constitute one of the sources of Co-58 and Co-60. However, there is no published mechanism explaining the formation of these filaments.
  • a significant proportion of the rate of oxidation of the material of the tube can be characterized by the rate of formation of the filaments 11, which form particularly when the rate of the primary medium is low, and when the primary medium tends to be saturated with nickel in ionic form.
  • the applicant has discovered that, surprisingly, it was possible to limit, or even prevent, the formation of the filaments 11 in a primary medium, and consequently to slow down or eliminate one of the forms of oxidation of the metallic material, by maintaining in the superficial metallic layer 7 a significant mass content of available chromium. Maintaining a low carbon content also contributes to preventing the formation of the filaments 11 when this can occur.
  • oxide or carbide particles whose solubility is greater than that of nickel oxides in the primary medium - in particular aluminum oxide particles, when they are substituted for the native oxide layer - contribute also to the formation of the filaments 11 in the primary medium when this can take place.
  • the oxide layer 3 does not contain any particle whose solubility is greater than that of nickel oxide compounds in the primary medium, and in particular no aluminum-rich particles.
  • the filaments are not always observable. It is preferable to work under specific conditions in a primary medium with low convection and low levels of dissolved iron, nickel, oxygen and chromium to obtain them.
  • a hydrogenated primary medium when the dissolved iron content is less than 1 ⁇ g/kg, the oxidation of the alloy is always at the origin of the formation of filaments.
  • the rate of oxidation in the filament forming zone controls the rate of filament formation, if one forms.
  • the filaments can be dissolved more quickly than they form and/or are torn off.
  • the applicant has in fact discovered that the formation of the filaments 11 results from the fact that, in the surface layer 7, the carbon content present in the carbides or outside the carbides, contributes to the formation of filaments . Moreover, in this layer a significant part of the chromium is present in the form of carbides. The chromium integrated into the carbides does not contribute, or contributes little, to preventing the formation of the filaments 11. On the contrary, the available chromium, that is to say not integrated into the carbides, contributes to preventing the formation of the filaments.
  • the zones where the filaments are formed are the zones most favorable to oxidation of the alloy and to relaxation, whatever its form (ions or colloids). These zones are characterized by a low level of available chromium and/or the presence of soluble oxides in the oxide layer.
  • the available chromium mass content is evaluated as follows.
  • w Cr (p) will be denoted the mass content of chromium in the superficial metallic layer at a depth p from the internal surface 5 of the tube, w c (p) the mass content of carbon in the superficial metallic layer at depth p, w Cr_carbide (p) the chromium content potentially integrated in the carbides assuming that the carbides have Cr 23 C 6 stoichiometry of the superficial metallic layer at depth p, and w Cr_dispo (p) the available chromium content of the superficial metallic layer at depth p.
  • the depth p is taken radially, from the inner surface 5, towards the base metal 9.
  • the mass content is defined here as being the mass of the chromium or carbon atoms divided by the mass of the superficial metallic layer, for a unit volume of the given superficial metallic layer.
  • Thermodynamically stable chromium carbide is considered here in the type of alloy considered for element 1, having the formula C 6 Cr 23 . It should be noted that this is an overriding assumption. There are other forms of carbides, consuming less chromium.
  • the molar masses of carbon and chromium are respectively 12 and 52.
  • the mass content of available chromium w Cr_dispo (p) at a depth p can have a negative value.
  • a negative value has no physical meaning, but expresses the magnitude of the chromium deficit not captured by the carbides or the magnitude of the excess carbon.
  • the mass content of available chromium taken on average over the entire thickness of the surface metallic layer 7 from the internal surface 5, is greater than 0.
  • This content of free chromium throughout the thickness of the superficial metal layer will make it possible to form during its oxidation a layer of oxide rich in chromium which will thus constitute a barrier effectively preventing the formation of nickel-rich filaments 11 and the release of colloidal or ionic compounds rich in nickel during the use of element 1 in a pressurized water nuclear reactor.
  • a high carbon or carbide content generally results from the hot transformation of impurities at the time of manufacture of the element 1, in particular of lubricant. It can also come from the fact that the casting alloy used for the manufacture of the tube itself had a high carbon content.
  • the superficial metallic layer 7 is depleted in chromium by dilution when the contents of the alloying elements other than chromium, and the contents of the minority compounds are concentrated towards the surface of the metal during manufacture, handling or oxidation of the material.
  • the available chromium content taken as an average over a thickness e from the internal surface 5, is called the average available chromium content over e in the following.
  • This thickness e is typically taken to be less than or equal to the thickness E of the surface metal layer 7.
  • the average chromium content available on e denoted w Cr_dispo e , is evaluated in the following manner.
  • the mass content of chromium w Cr (p) and/or the mass content of carbon w c (p) is measured at different depths p of the surface metallic layer 7, on a sample of the element 1.
  • This sample has for example a diameter of 20 ⁇ 1 mm at the level of the internal surface and a thickness of 1mm.
  • the superficial metallic layer is analyzed at 100 different depths, distributed between 0 and e.
  • the retained mass contents w Cr (p) and/or w c (p) correspond for example to the average of the measurement results.
  • the mass content of chromium and/or carbon is measured by glow discharge spectrometry (SDL, GDOES in English). This technique is known and will not be detailed here.
  • the mass content of chromium and/or carbon is measured by Auger spectrometry or X photoelectron spectrometry coupled with a method of abrasion of the internal surface of the tube (for example ion abrasion).
  • the mass content of chromium and/or carbon is measured by ray spectroscopy Energy Dispersive X-ray Spectroscopy (EDS) on a transverse section (or microscopic slide obtained by focused ion probe) of the tube studied by scanning electron microscope (SEM) or transmission ( MET).
  • EDS ray spectroscopy Energy Dispersive X-ray Spectroscopy
  • SEM scanning electron microscope
  • MET transmission
  • a weight practically equal to 0 is thus assigned to the measurements carried out on carbonaceous impurities generally present on the metallographic preparations, and to the measurements carried out in the superficial metallic layer a weight practically equal to 1 is assigned.
  • the element 1 of the invention is such that the mass content of available chromium, taken on average over the entire thickness E of the surface metal layer 7, from the internal surface 5, is greater to 0.
  • element 1 of the invention is such that the chromium content available in the superficial metallic layer 7, taken on average over 200 nm of thickness of the superficial metallic layer 7 from the internal surface 5, is greater than 0.
  • element 1 of the invention is such that the mass content of available chromium, taken as an average over the thickness E of the surface layer 7 and/or over a thickness of 200 nm of the surface metal layer 7 from the internal surface 5, is greater than 0.
  • the element 1 of the invention is such that the chromium content available in the surface metallic layer 7, taken on average over a thickness of 10 nm of surface metal layer 7 from inner surface 5, is greater than 0.
  • element 1 of the invention is such that the mass content of available chromium, taken as an average over the thickness E of the surface layer 7 and/or over a thickness of 200 nm and/or over a thickness of 10 nm of the superficial metallic layer 7 starting from the internal surface 5, is greater than 0.
  • the element 1 of the invention is such that the chromium content available in the superficial metallic layer 7, taken on average over a thickness of 1 nm of the superficial metallic layer 7 starting from the internal surface 5, is greater than 0.
  • the average available chromium contents over the thickness E, and/or 200 nm, and/or 10 nm, and/or 1 nm are greater than 0.
  • the average available chromium contents over E , and/or 200 nm, and/or 10 nm, and/or 1 nm are greater than 5%, more preferably greater than 15%.
  • the average available chromium contents over E, and/or 200 nm, and/or 10 nm and/or 1 nm are calculated by averaging the available chromium mass contents w Cr_dispo (p), and not the standardized mass contents in chrome available W N_Cr_dispo (p).
  • element 1 of the invention preferably has an available chromium content w Cr_dispo (p) which is constantly greater than 0 throughout the entire thickness of surface metallic layer 7.
  • the surface metal layer 7 always has an available chromium content w Cr_dispo (p) greater than 0.
  • This available chromium content w Cr_dispo (p) is preferably greater than 5%, still preferably greater than 15%, whatever the depth p.
  • the available chromium content w Cr_dispo (p) in the surface metallic layer 7 is constantly greater than 0 in a thickness of 200 nm starting from the internal surface 5, and/or in a thickness of 10 nm starting from the internal surface 5, and/or in a thickness of 1 nm from the internal surface 5.
  • the available chromium content is constantly greater than 5%, more preferably constantly greater than 15%, in a thickness of 200 nm starting from the internal surface 5, and/or in a thickness of 10 nm starting from the internal surface 5, and/or in a thickness of 1 nm from the internal surface 5
  • the picture 2 represents the mass content of chromium w Cr (p) (curve 1), and the normalized mass content of available chromium w N_Cr_dispo (p) (curve 2), as a function of the depth from the internal surface, for a piece of new steam generator tube. It can be seen that there is in this tube a strong deficit of chromium available between 0 and 10 nm.
  • the mass content of available chromium is negative up to 10 nm, and remains less than 15% down to a depth of approximately 50 nm.
  • a negative value of the mass content of available chromium has no physical meaning, a negative value expresses the magnitude of the chromium deficit not captured by the carbides or the magnitude of the excess carbon.
  • the picture 3 represents the standardized mass contents of available chromium w N_Cr_available (p), as a function of the depth from the internal surface, for sections coming from different steam generator tubes. These tubes are new and have been manufactured by different suppliers. They are intended to equip steam generators of new nuclear reactors, or new steam generators installed as a replacement on old reactors.
  • the surface metallic layer 7 has a composition which deviates from the composition of the nickel-based alloy, while remaining close to it. It has mass contents which are slightly different from those of the base metal, i.e. the nickel-based alloy, resulting from the treatments applied during the manufacture of element 1.
  • the content of chromium w Cr (p), taken on average over the entire thickness of the superficial metallic layer 7 starting from the internal surface 5, is less than 45%. It is typically between 20 and 32% over the first 200 nanometers.
  • This content of chromium w Cr (p) increases, from the internal surface 5, over the entire thickness of the surface metallic layer 7. It is typically between 0.1% and 20% on the internal surface 5. It increases constantly when the depth p increases. It is close to the content of the nickel base alloy at a depth of 100 nm. Typically, the difference between the chromium content of the nickel base alloy and the chromium content of the surface layer is less than 30%, preferably less than 5%, at a depth of 100 nm.
  • the nickel content taken on average over the entire thickness of the surface metallic layer 7 starting from the internal surface 5, is greater than 1%. It is typically greater than 40%.
  • the nickel content, taken on average over 100 nm from the internal surface 5, is greater than 40%, typically greater than 45%.
  • the steam generators of the invention are capable of being manufactured using different methods.
  • the untreated element is in the nickel-based alloy defined above. It is manufactured by any suitable method. It is for example extruded, rolled from an ingot, rolled, welded etc.
  • the internal surface 5 delimits the internal side of the tube, that is to say the internal passage of the tube.
  • the surface treatment aims to eliminate or replace a thin layer of the internal surface 5 of the untreated element, which has a deficit of available chromium.
  • the surface treatment aims to eliminate or replace part of the surface metallic layer 7, which has a low available chromium content.
  • the surface treatment aims to remove or replace the entire surface metal layer 7.
  • the surface treatment aims to eliminate or replace part of the superficial metallic layer 7 of thickness chosen so that the average chromium content available over the entire thickness E of the superficial metallic layer 7 w Cr_dispo E is below a predetermined limit, after application of the surface treatment.
  • the predetermined limit is for example 0%, 5% or 15%. It is also possible to consider the average chromium content available over 200 nm, or over 10 nm, or over 1 nm instead of the average chromium content available over the entire thickness of the surface metallic layer 7.
  • the surface treatment also aims to remove unwanted compounds in the oxide layer, including alumina.
  • a treatment can be obtained for example by chemical cleaning in a heated alkaline solution.
  • the thickness of the layer stripped by surface treatment is chosen on a case-by-case basis, after analysis of the profile of the mass content of chromium available as a function of the depth from the internal surface of the untreated element. .
  • This profile depends on the alloy used for the manufacture of the untreated element, and on the method of manufacture. For example, this thickness is less than 1 ⁇ m, preferably less than 200 nm, more preferably less than 100 nm.
  • Electropolishing is an electrochemical surface treatment process by which the metal of the surface layer is removed by anodic dissolution. Certain elements of the alloy partially insoluble in the electropolishing bath - in particular chromium oxide - remain on the surface of the part and form a protective barrier.
  • Mechanical polishing consists in stripping the part by an abrasive means. Many means can be used: circulating a liquid loaded with abrasive particles in contact with the surface, moving an abrasive member such as a disc, a brush, etc. in contact with the surface.
  • Chemical cleaning is a technique consisting in bringing the surface to be treated into contact with a chemical solution of composition chosen to dissolve the superficial layer of the surface.
  • the chemical solution comprises, for example, concentrated acids and complexing agents making it possible to increase the solubility of certain oxides.
  • Chemical-mechanical polishing combines mechanical polishing and chemical cleaning.
  • a chemical solution loaded with abrasive particles is circulated in contact with the surface to be treated.
  • the Struers company markets polishing suspensions suitable for such operations, for example the suspensions sold under the name OP-AA and OP-S which are solutions of acids or bases, complexing agents and colloidal suspensions of abrasive oxides silicone or alumina.
  • the untreated element becomes said element described above, having the available chromium content required by the invention.
  • the surface treatment is carried out on the untreated element, before final assembly in the steam generator.
  • the chemical composition used in this case is compatible with all the requirements relating to the chemistry of the primary circuit.
  • the solution includes boric acid, and/or peroxides.
  • the surface treatment is carried out in the nuclear power plant, once the steam generator is permanently connected to the primary circuit.
  • the treatment in this case is mechanical or chemical-mechanical polishing, or chemical cleaning.
  • the steam generator in this case is not yet connected to the primary circuit of the nuclear reactor.
  • the processing is for example carried out in the steam generator manufacturing workshop, which is not on the site of the nuclear power plant.
  • the method comprising a step of manufacturing the element by rolling an ingot with a non-carbon lubricant or by continuous casting then rolling with a non-carbon lubricant.
  • the ingot is in the nickel-based alloy described above. Before rolling, it has the shape of a hollow cylinder in the case where the element is a tube.
  • non-carbon liquids can be used as lubricants including certain molten salts, low melting point metals or many aqueous solutions.
  • the lubricant used is non-carbonaceous, the amount of carbon on the inner surface of the tube is reduced, and the amount of chromium carbides on the inner surface of the tube is also reduced. As a result, the amount of available chromium is increased.
  • the element having the available chromium content required by the invention is a tube
  • the latter is mounted in the steam generator as shown in the figure 4 .
  • the steam generator 13 comprises an outer envelope 15, and a tube sheet 17 dividing the internal volume of the envelope into a water box 19 and an upper volume 21.
  • the water box 17 is divided by an internal partition 22 into an upstream compartment 23 and a downstream compartment 25.
  • the steam generator has a secondary liquid inlet 27 and a steam outlet 29, both opening into the upper volume 21. They are respectively connected to a secondary pump and to a steam turbine.
  • the tubes 1 each open via an upstream end into the upstream compartment 23 of the water box, and via a downstream end opposite the upstream end into the downstream compartment 25.
  • the tubes each have a U-shape and their ends are rigidly fixed to the tube sheet 17.
  • the upstream compartment 23 is fluidically connected to an outlet 31 of a vessel 33 of the nuclear reactor.
  • the downstream compartment 25 is fluidically connected to an inlet 35 of the vessel 33 of the nuclear reactor.
  • the primary liquid is heated in the reactor vessel, then circulates to the upstream compartment of the water box. He then circulates from the upstream compartment to the downstream compartment, inside the tubes 1. It transfers part of its thermal energy to the secondary liquid in passing. It then circulates from the downstream compartment to the inlet of the tank.
  • the element having the available chromium content required by the invention is a plate mounted in the steam generator, one internal surface of which is in contact with the primary fluid.
  • This plate is for example the plate 22 separating the upstream and downstream compartments from each other.
  • the surface treatment is provided to etch the internal surface until the mass content of available chromium w Cr_dispo (p), taken on average over the entire thickness of the surface metal layer 7 from the internal surface 5, is greater than 0, with the aim of limiting the oxidation liable to lead to the formation of filaments rich in nickel 11, and/or the direct release into the primary liquid of the nuclear reactor of ions or colloids originating from the zones where these Filaments are liable to form when the internal surface 5 is exposed to the primary liquid of the pressurized water reactor during the energy production phases, that is to say during nominal operation of the nuclear reactor.
  • the primary liquid considered here meets the specifications of the main reactor operators or the main research and safety organizations in the field.
  • it has a nickel (ion) content less than or equal to the lowest published solubility limit, the flow being characterized by a Reynolds number between 0 and 10 6 .
  • nickel-rich filament here means a filament comprising more than 50% nickel by mass.
  • the alloy is typically one of the alloys defined above.
  • the surface treatment is one of the surface treatments defined above.
  • the surface treatment is used until the mass content of available chromium w Cr_dispo (p), taken as an average over a thickness of 200 nm from the internal surface 5, and/or taken as an average over a thickness 10 nm from the internal surface 5, and/or taken on average over a thickness of 1 nm from the internal surface 5, ie greater than 0, still for the same purpose.
  • the surface treatment is used until the mass content of available chromium w Cr_dispo (p), taken on average over the entire thickness of the surface metallic layer, and/or 200 nm, and/or 10 nm, and/or over 1 nm from the internal surface, ie greater than 5%, more preferably than 15%.
  • the invention also relates to the use of a steam generator as described above in a pressurized water nuclear reactor, with the aim of avoiding the formation on the internal surface 5 of the element of filaments whose composition by mass is rich in nickel and/or the direct release into a primary liquid of the nuclear reactor of colloids originating from these filaments 11, when the internal surface 5 is exposed to the primary liquid during nominal operation of the nuclear reactor.
  • the element 1 is for example a tube 1 which is used for the circulation of the primary liquid of the nuclear reactor during the normal operation of the reactor, from the upstream compartment 23 of the water box 19 to the downstream compartment 25, or a plate.
  • the primary liquid considered here is as described above.
  • the manufacturing methods of the invention are particularly advantageous because they do not create any heating of the material constituting the untreated element. This retains its initial microstructure. This is particularly important for the steam generator tubes, which are for example made of a 690TT alloy. This alloy is subjected, before the surface treatment step described here, to a defined heat treatment, aimed in particular at forming intergranular chromium carbides while maintaining a grain size of the metal within a precise range. Excessive heating of the tube during the surface treatment, bringing the alloy to more than 800° C. for example, would cause at least part of the benefit of the heat treatment to be lost or would cause a change in the size of the grains of the metal.
  • most of the surface treatments considered in the invention are carried out by causing a fluid to circulate in contact with the internal surface of the element to be treated.
  • the fluid is propelled for example by a pump or a swab or a wad of felt pushed by means of a compressed gas.
  • the implementation of these treatments by circulation is much simpler than that of treatment of the plasma deposition type, or other similar treatment, for steam generator tubes. These tubes are of long lengths, more than 20 m, and small external diameters, less than 20 mm. He To date, there is no enclosure allowing deposits to be made by PVD (Physical Vapor Deposition) on the internal surface of this type of part.
  • PVD Physical Vapor Deposition
  • Treatments aimed at eliminating part of the surface metallic layer are particularly advantageous. They are simpler to implement than those involving a deposition on the surface metal layer. There is no risk that the deposited material will present cracks, or that there will be decohesions at the interface between the surface metallic layer and the deposited material.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
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  • Other Surface Treatments For Metallic Materials (AREA)
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EP15845497.5A 2015-11-24 2015-11-24 Générateur de vapeur, procédés de fabrication et utilisations correspondantes Active EP3380787B1 (fr)

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JP4042362B2 (ja) * 2000-08-11 2008-02-06 住友金属工業株式会社 Ｎｉ基合金製品とその製造方法
US6488783B1 (en) * 2001-03-30 2002-12-03 Babcock & Wilcox Canada, Ltd. High temperature gaseous oxidation for passivation of austenitic alloys
US20100032061A1 (en) * 2005-02-04 2010-02-11 Hiroyuki Anada METHOD FOR MANUFACTURING A Ni-BASED ALLOY ARTICLE AND PRODUCT THEREFROM
JP2006292531A (ja) * 2005-04-11 2006-10-26 Mitsubishi Heavy Ind Ltd 蒸気発生器用伝熱管の表面処理方法
JP4586938B2 (ja) * 2009-02-16 2010-11-24 住友金属工業株式会社 金属管の製造方法
KR101516505B1 (ko) * 2010-08-26 2015-05-04 신닛테츠스미킨 카부시키카이샤 Cr함유 오스테나이트 합금관 및 그 제조 방법
WO2013002314A1 (ja) * 2011-06-29 2013-01-03 新日鐵住金株式会社 原子力発電プラント用蒸気発生器伝熱管の製造方法および蒸気発生器伝熱管
ES2706182T3 (es) * 2012-03-28 2019-03-27 Nippon Steel & Sumitomo Metal Corp Aleación austenitica que contiene Cr
CN103594127A (zh) * 2013-11-13 2014-02-19 南通曙光新能源装备有限公司 一种节能核电蒸发器
JP2015110818A (ja) * 2013-12-06 2015-06-18 株式会社東芝 蒸気発生器の伝熱管の表面処理方法及び表面処理システム
CN203931515U (zh) * 2014-03-20 2014-11-05 中国核动力研究设计院 基于177堆芯的能动加非能动核蒸汽供应系统及其核电站

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WO2017089658A1 (fr) 2017-06-01
ES2930449T3 (es) 2022-12-13
JP6850800B2 (ja) 2021-03-31
EP3380787A1 (fr) 2018-10-03
JP2019502106A (ja) 2019-01-24
CN108700285B (zh) 2020-07-28

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