JP5242610B2 - Structural material surface modification apparatus and method - Google Patents

Structural material surface modification apparatus and method Download PDF

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JP5242610B2
JP5242610B2 JP2010045415A JP2010045415A JP5242610B2 JP 5242610 B2 JP5242610 B2 JP 5242610B2 JP 2010045415 A JP2010045415 A JP 2010045415A JP 2010045415 A JP2010045415 A JP 2010045415A JP 5242610 B2 JP5242610 B2 JP 5242610B2
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torch part
surface modification
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俊幸 田澤
利恵 角谷
基司 坪田
千尋 楢崎
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Toshiba Corp
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Description

本発明は、原子力プラント等に用いられる構造材の表面改質装置及びその方法に関する。   The present invention relates to a structural material surface reforming apparatus and method used in a nuclear power plant or the like.

原子力プラントにおいて、炉内構造物、配管、タービン等の構造物には溶接部も含めて主にステンレス鋼やニッケル基合金が材料として用いられている。これらの金属材料においては、プラント運転時における各々の環境に応じた劣化がしばしば問題となり、この問題の対策として金属材料に表面処理を施工することで材料改善をする技術が用いられている。   In nuclear power plants, structures such as in-furnace structures, piping, and turbines, including welds, are mainly made of stainless steel or nickel-based alloys. In these metal materials, deterioration according to each environment during plant operation often becomes a problem, and a technique for improving the material by applying a surface treatment to the metal material is used as a countermeasure for this problem.

特に、ニッケル基合金は溶接熱影響部だけでなく、溶接金属部における応力腐食割れの発生事例も報告されており、溶接金属および溶接熱影響部の双方において耐食性の向上が求められる。現在のところ、軽水炉発電プラントの構造物における応力腐食割れ対策技術として、金属材料にピーニングを施工する技術が提案されている（特許文献１、２）。   In particular, nickel-base alloys have been reported not only in the heat affected zone but also in stress corrosion cracks in the weld metal, and it is required to improve the corrosion resistance in both the weld metal and the weld heat affected zone. At present, as a technique for preventing stress corrosion cracking in a structure of a light water reactor power plant, a technique for peening a metal material has been proposed (Patent Documents 1 and 2).

他にも金属表面に酸化チタンのような光触媒をコーティングし、光の照射下で表面電位を低減させることにより、耐食性を向上させるような技術（特許文献３）や、肉盛溶接を施工することで耐食性を向上させる技術も提案されている（特許文献４）。   In addition, by applying a photocatalyst such as titanium oxide on the metal surface and reducing the surface potential under light irradiation, a technique to improve corrosion resistance (Patent Document 3) and overlay welding A technique for improving the corrosion resistance is also proposed (Patent Document 4).

特開２００９−２１０８２５号公報JP 2009-210825A 特開２００７−４４６９８号公報JP 2007-44698 A 特開２００８−２７４４１９号公報JP 2008-274419 A 特開平１０−２６０２９０号公報JP-A-10-260290

上記特許文献１又は２に記載される従来のピーニングによる応力腐食割れ予防技術は、溶接施工が完了した後に独立して行うものである。すなわち、溶接が完了しない限り実施できず、溶接からピーニングへの工程の移行に伴う装置の入れ換え作業や調整が必要となるため、工期が長期間に及ぶという問題があった。   The conventional technique for preventing stress corrosion cracking by peening described in Patent Document 1 or 2 is performed independently after welding is completed. That is, it cannot be performed unless the welding is completed, and it is necessary to replace and adjust the apparatus accompanying the transition from the welding to the peening process.

また、特許文献３に記載されるコーティングによる耐食技術も同様に、製造工程の最終工程において独立して行う作業であるとともに、光触媒活性度の高いアナターゼ型酸化チタンをゾルゲル法で得るためには、基材を４００℃以上に加熱しなければならないため、別途加熱処理が必要である。また装置の入れ換え作業や調節が必要であるため、工期期間が長期に及ぶ可能性があった。   Similarly, the anticorrosion technology by coating described in Patent Document 3 is also an operation performed independently in the final step of the manufacturing process, and in order to obtain anatase-type titanium oxide with high photocatalytic activity by the sol-gel method, Since the substrate must be heated to 400 ° C. or higher, a separate heat treatment is required. Moreover, since the work for replacing and adjusting the apparatus is necessary, the construction period may be long.

さらに、特許文献４は肉盛溶接を用いた表面改質技術であるが、溶接条件が変わること、肉盛溶接の溶接金属を別に用意する必要があること、また、その際に溶接金属を交換し条件設定をするか、場合によっては溶接機の入れ換えが必要なこともあることなどの理由により、同様に、長期の工期期間を必要とするものである。   Furthermore, Patent Document 4 is a surface modification technique using overlay welding. However, it is necessary to prepare welding metal for overlay welding, which requires different welding conditions, and replacement of the welding metal. However, it also requires a long construction period due to the fact that the conditions are set or the welding machine may need to be replaced in some cases.

本発明は上記課題を解決するためになされたもので、簡便で小型の溶接改質装置により、短期間で効率的に溶接金属の耐食性を改善することができる構造材の表面改質装置及びその方法を提供することを目的とする。   SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problems. A surface modification device for a structural material that can efficiently improve the corrosion resistance of a weld metal in a short period of time with a simple and small welding reformer, and its It aims to provide a method.

上記課題を解決するために、本発明に係る構造材の表面改質装置は、溶接トーチ部と表面改質トーチ部とを有する構造材の表面改質装置において、前記溶接トーチ部と表面改質トーチ部を移動可能な連結部材により連結するとともに、前記表面改質トーチ部は、前記溶接トーチ部で形成された溶接金属の表面にチタン含有溶液を噴射しアナターゼ型酸化チタン層を形成することを特徴とする。   In order to solve the above problems, a structural material surface modification device according to the present invention is a structural material surface modification device having a welding torch part and a surface modification torch part. The torch part is connected by a movable connecting member, and the surface-modified torch part forms an anatase-type titanium oxide layer by injecting a titanium-containing solution onto the surface of the weld metal formed by the welding torch part. Features.

また、本発明に係る構造材の表面改質装置は、溶接トーチ部と溶射トーチ部とを有する構造材の表面改質装置において、前記溶接トーチ部と溶射トーチ部を移動可能な連結部材により連結するとともに、前記溶射トーチ部は、前記溶接トーチ部で形成された溶接金属の表面にアナターゼ型酸化チタン粉末からなる溶射材をガスフレーム溶射により噴射しアナターゼ型酸化チタン層を形成することを特徴とする。   The structural material surface modifying apparatus according to the present invention is a structural material surface modifying apparatus having a welding torch part and a thermal spraying torch part, wherein the welding torch part and the thermal spraying torch part are connected by a movable connecting member. The spraying torch part is characterized in that an anatase-type titanium oxide layer is formed by spraying a sprayed material made of anatase-type titanium oxide powder on the surface of the weld metal formed by the welding torch part by gas flame spraying. To do.

また、本発明に係る構造材の表面改質方法は、本発明に係る表面改質装置を用いて、構造材の溶接金属の表面にアナターゼ型酸化チタン又は貴金属からなる表面改質層を形成することを特徴とする。   Moreover, the surface modification method for a structural material according to the present invention uses the surface modification device according to the present invention to form a surface modified layer made of anatase titanium oxide or a noble metal on the surface of the weld metal of the structural material. It is characterized by that.

本発明によれば、簡便で小型の溶接改質装置により、短期間で溶接金属の耐食性を改善することができる構造材の表面改質装置及びその方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the surface modification apparatus of the structural material which can improve the corrosion resistance of a weld metal in a short period of time with a simple and small welding reformer, and its method can be provided.

本発明の第１の実施形態に係る表面改質装置の全体構成図。1 is an overall configuration diagram of a surface modification apparatus according to a first embodiment of the present invention. （ａ）は溶接金属の表面に形成された表面改質層を示す図、（ｂ）はその断面図。(A) is a figure which shows the surface modification layer formed in the surface of a weld metal, (b) is the sectional drawing. 本発明の第２の実施形態に係る表面改質トーチ部の構成図。The block diagram of the surface modification torch part which concerns on the 2nd Embodiment of this invention. 本発明の第３の実施形態に係る表面改質装置の全体構成図。The whole block diagram of the surface modification device concerning a 3rd embodiment of the present invention. （ａ）は溶接金属の表面に形成された表面改質層を示す図、（ｂ）はその断面図。(A) is a figure which shows the surface modification layer formed in the surface of a weld metal, (b) is the sectional drawing.

本発明に係る構造材の表面改質装置及びその方法の実施形態を、図面を参照して説明する。
（第１の実施形態）
本発明の第１の実施形態に係るプラント構造材の表面改質装置を図１及び図２を用いて説明する。 Embodiments of a surface modification apparatus and method for a structural material according to the present invention will be described with reference to the drawings.
(First embodiment)
A plant structural material surface reforming apparatus according to a first embodiment of the present invention will be described with reference to FIGS. 1 and 2.

図１において、本実施形態に係る表面改質装置１は、電極１１とガスノズル１２とフィラーワイヤー１３からなる溶接トーチ部２と、溶液タンク１４とスプレーノズル１５と溶液１６からなる表面改質トーチ部３と、この溶接トーチ部２と表面改質トーチ部３とを連結する連結部材１７と、構造材からなる被溶接材１８とから構成される。   In FIG. 1, the surface modification device 1 according to this embodiment includes a welding torch unit 2 including an electrode 11, a gas nozzle 12, and a filler wire 13, and a surface modification torch unit including a solution tank 14, a spray nozzle 15, and a solution 16. 3, a connecting member 17 that connects the welding torch part 2 and the surface modified torch part 3, and a material to be welded 18 made of a structural material.

表面改質トーチ部３は、連結部材１７によって溶接方向に対して上下方向および前後方向に移動可能であり、被溶接材１８の施工面との距離および溶接トーチ部２との距離をそれぞれ変えることができる。   The surface-modified torch part 3 can be moved in the vertical direction and the front-rear direction with respect to the welding direction by the connecting member 17, and the distance from the construction surface of the workpiece 18 and the distance from the welding torch part 2 can be changed. Can do.

本実施形態では、溶液１６には例えばチタンテトライソプロポキシドのエタノール溶液からなるゾルゲル溶液を、溶接金属にはニッケル基合金を用い、溶接方法はティグ溶接を用いている。なお、スプレーノズル１５の代わりに、滴下式や流出式のノズルを用いてもよい。   In this embodiment, a sol-gel solution made of, for example, an ethanol solution of titanium tetraisopropoxide is used as the solution 16, a nickel-based alloy is used as the weld metal, and TIG welding is used as the welding method. Instead of the spray nozzle 15, a dripping type or outflow type nozzle may be used.

このように構成された表面改質装置１において、溶接トーチ部２でニッケル基合金のティグ溶接を行いながら、溶接金属２２の表面に対して、表面改質トーチ部３の溶液１６をスプレーノズル１５から垂直に連続噴霧する。   In the surface modification device 1 configured in this way, the solution 16 in the surface modification torch part 3 is sprayed on the surface of the weld metal 22 while performing the TIG welding of the nickel base alloy in the welding torch part 2. Spray continuously vertically.

その際、溶接金属２２の表面の温度は、溶接工程の余熱により４００℃以上に保持されているため、図２（ａ）、（ｂ）に示すようにアナターゼ型酸化チタンの表面改質層２１が、ゾルゲル法の原理により、溶接金属２２およびその近傍の溶接熱影響部の表面に成膜される。   At that time, the temperature of the surface of the weld metal 22 is maintained at 400 ° C. or higher due to the residual heat of the welding process. Therefore, as shown in FIGS. However, the film is formed on the surface of the weld metal 22 and the weld heat affected zone in the vicinity thereof by the principle of the sol-gel method.

このアナターゼ型酸化チタンは光触媒作用に優れており、プラント稼働中に、アナターゼ型酸化チタン表面に原子炉内で発生するチェレンコフ光のようなアナターゼ型酸化チタンのバンドギャップエネルギーよりも高いエネルギーを持った光が照射されれば光触媒反応が生じ、表面の電位が低減する。この表面電位、すなわち腐食電位の低減によって耐食性が向上する。
このように本実施形態では、従来必要とされた余熱工程を省略することができるので、工期を大幅に短縮することが可能となる。 This anatase-type titanium oxide has excellent photocatalytic action, and has higher energy than the band gap energy of anatase-type titanium oxide such as Cherenkov light generated in the reactor on the surface of anatase-type titanium oxide during plant operation. When light is irradiated, a photocatalytic reaction occurs and the surface potential is reduced. Corrosion resistance is improved by reducing the surface potential, that is, the corrosion potential.
As described above, in the present embodiment, the preheating process that has been conventionally required can be omitted, so that the construction period can be significantly shortened.

以上説明したように、本第１の実施形態によれば、溶接トーチ部２と表面改質トーチ部３が連結された小型の表面改質装置１を用いて、溶接工程とその溶接熱を利用した表面改質工程を連続的におこなうことにより、溶接金属の表面にアナターゼ型酸化チタン層からなる表面改質層２１を効率的かつ短期間で形成することができる。   As described above, according to the first embodiment, the welding process and its welding heat are used by using the small surface modification device 1 in which the welding torch part 2 and the surface modification torch part 3 are connected. By continuously performing the surface modification step, the surface modification layer 21 composed of the anatase-type titanium oxide layer can be efficiently and quickly formed on the surface of the weld metal.

（第２の実施形態）
本発明の第２の実施形態に係る構造材の表面改質装置を、図３を用いて説明する。
本第２の実施形態は、第１の実施形態における表面改質トーチ部３として溶射トーチ部４を用いている。この溶射トーチ部４は、熱源３１と、溶射材供給系統３２と、キャリアガスを流出するキャリアガスノズル３３と、カバー３４と、溶射材３５とから構成される。この溶射トーチ部４は、第１の実施形態と同様に溶接トーチ部２に連結部材１７により連結され、溶接方向に対して上下方向および前後方向に移動可能である。 (Second Embodiment)
A structural material surface reforming apparatus according to a second embodiment of the present invention will be described with reference to FIG.
In the second embodiment, the thermal spraying torch part 4 is used as the surface modifying torch part 3 in the first embodiment. The thermal spray torch unit 4 includes a heat source 31, a thermal spray material supply system 32, a carrier gas nozzle 33 that flows out a carrier gas, a cover 34, and a thermal spray material 35. The thermal spray torch part 4 is connected to the welding torch part 2 by a connecting member 17 as in the first embodiment, and is movable in the vertical direction and the front-rear direction with respect to the welding direction.

本実施形態において、溶射方法は燃焼ガスと酸素の燃焼フレームを熱源とした高速ガスフレーム溶射とし、燃焼ガスとしてアセチレン（Ｃ２Ｈ２）とプロピレン（Ｃ３Ｈ６）の混合ガスを、溶射材３５としてアナターゼ型酸化チタン粉末を、キャリアガスとして窒素を用いている。また、溶接金属２２はニッケル基合金を用い、溶接方法はティグ溶接を用いている。 In this embodiment, the thermal spraying method is high-speed gas flame spraying using a combustion flame of combustion gas and oxygen as a heat source, and a mixed gas of acetylene (C 2 H 2 ) and propylene (C 3 H 6 ) is used as the thermal spray. Anatase-type titanium oxide powder 35 is used, and nitrogen is used as a carrier gas. Further, the weld metal 22 uses a nickel base alloy, and the welding method uses TIG welding.

このように構成された表面改質装置１において、溶接トーチ部１でアーク溶接を行いながら、溶接金属２２の表面に対して高速ガスフレーム溶射を行うと、図２（ａ）、（ｂ）に示すように溶接金属２２およびその近傍の溶接熱影響部の表面にアナターゼ型酸化チタンの表面改質層２１が形成される。   When the high-speed gas flame spraying is performed on the surface of the weld metal 22 while performing the arc welding in the welding torch portion 1 in the surface modification device 1 configured in this way, FIGS. 2 (a) and 2 (b). As shown, a surface modified layer 21 of anatase-type titanium oxide is formed on the surface of the weld metal 22 and the weld heat affected zone in the vicinity thereof.

本第２の実施形態によれば、溶接トーチ部２と溶射トーチ部４が連結された小型の表面改質装置１を用いて、溶接工程とその溶接熱を利用した表面改質工程を連続的におこなうことにより、溶接金属の表面にアナターゼ型酸化チタン層からなる表面改質層２１を効率的かつ短期間で形成することができる。   According to the second embodiment, the welding process and the surface modification process using the welding heat are continuously performed using the small surface modification apparatus 1 in which the welding torch part 2 and the thermal spraying torch part 4 are connected. By performing the above, the surface modification layer 21 made of an anatase-type titanium oxide layer can be efficiently and quickly formed on the surface of the weld metal.

（第３の実施形態）
本発明の第３の実施形態に係る構造材の表面改質装置を、図４、図５を用いて説明する。
本第３の実施形態では、表面改質装置１としてガスシールドアーク溶接を用い、溶接と表面改質層の形成を連続的におこなっている。 (Third embodiment)
A structural material surface modification apparatus according to a third embodiment of the present invention will be described with reference to FIGS.
In the third embodiment, gas shield arc welding is used as the surface modification device 1, and welding and surface modification layer formation are continuously performed.

図４において、本実施形態に係る表面改質装置１は、電極１１とガスノズル１２とフィラーワイヤー１３とガスボンベ４１とから構成され、フィラーワイヤー１３にはチタン元素を含有させ、ガスボンベ４１には酸素とアルゴンの混合ガスを用いている。   In FIG. 4, the surface modification apparatus 1 according to this embodiment includes an electrode 11, a gas nozzle 12, a filler wire 13, and a gas cylinder 41. The filler wire 13 contains a titanium element, and the gas cylinder 41 contains oxygen. A mixed gas of argon is used.

このようにして構成された表面改質装置１において、ガスシールドアーク溶接を行うと、シールドガスに添加した酸素がアークプラズマに晒されることによって、イオン、ラジカル等化学的に活性な種になり、この酸素の活性種と溶融池に含まれるチタン元素との化学結合によって、図５（ａ）、（ｂ）に示すように溶接金属２２の表面に表面改質層５１としてアナターゼ型酸化チタン層が形成される。   In the surface modification device 1 configured in this way, when gas shield arc welding is performed, oxygen added to the shield gas is exposed to arc plasma, thereby becoming a chemically active species such as ions and radicals, Due to the chemical bond between the active species of oxygen and the titanium element contained in the molten pool, an anatase-type titanium oxide layer is formed as a surface modification layer 51 on the surface of the weld metal 22 as shown in FIGS. 5 (a) and 5 (b). It is formed.

本第３の実施形態によれば、小型の表面改質装置１を用いて、溶接工程とその溶接熱を利用した表面改質工程を連続的におこなうことにより、溶接金属の表面にアナターゼ型酸化チタン層からなる表面改質層２１を効率的かつ短期間で形成することができる。   According to the third embodiment, the anatase-type oxidation is performed on the surface of the weld metal by continuously performing the welding process and the surface modification process using the welding heat using the small surface modification apparatus 1. The surface modification layer 21 made of a titanium layer can be formed efficiently and in a short period of time.

なお、上記実施形態では、溶接金属および被溶接材の表面にアナターゼ型酸化チタン層を形成する例を説明したが、チタンに限定されることはなく、例えばパラジウム（Ｐｄ）、イリジウム（Ｉｒ）、白金（Ｐｔ）、金（Ａｕ）などの貴金属を用いて表面改質層を形成しても同様の効果が得られる。   In the above embodiment, the example in which the anatase-type titanium oxide layer is formed on the surfaces of the weld metal and the workpiece to be welded has been described. However, the present invention is not limited to titanium. For example, palladium (Pd), iridium (Ir), The same effect can be obtained even if the surface modification layer is formed using a noble metal such as platinum (Pt) or gold (Au).

１…表面改質装置、２…溶接トーチ部、３…表面改質トーチ部、４…溶射トーチ部、１１…電極、１２…ガスノズル、１３…フィラーワイヤー、１４…溶液タンク、１５…スプレーノズル、１６…溶液、１７…連結部材、１８…被溶接材、２１…表面改質層、２２…溶接金属、３１…熱源、３２…溶射材供給系統、３３…キャリアガスノズル、３４…カバー、３５…溶射材、４１…ガスボンベ、５１…表面改質層。 DESCRIPTION OF SYMBOLS 1 ... Surface modification apparatus, 2 ... Welding torch part, 3 ... Surface modification torch part, 4 ... Spraying torch part, 11 ... Electrode, 12 ... Gas nozzle, 13 ... Filler wire, 14 ... Solution tank, 15 ... Spray nozzle, DESCRIPTION OF SYMBOLS 16 ... Solution, 17 ... Connecting member, 18 ... Material to be welded, 21 ... Surface modification layer, 22 ... Weld metal, 31 ... Heat source, 32 ... Spraying material supply system, 33 ... Carrier gas nozzle, 34 ... Cover, 35 ... Thermal spraying 41, gas cylinder, 51 ... surface modification layer.

Claims (7)

溶接トーチ部と表面改質トーチ部とを有する構造材の表面改質装置において、
前記溶接トーチ部と表面改質トーチ部を移動可能な連結部材により連結するとともに、前記表面改質トーチ部は、前記溶接トーチ部で形成された溶接金属の表面にチタン含有溶液を噴射しアナターゼ型酸化チタン層を形成することを特徴とする構造材の表面改質装置。 In the structural material surface modification apparatus having a welding torch part and a surface modification torch part,
The welding torch part and the surface modified torch part are connected by a movable connecting member, and the surface modified torch part sprays a titanium-containing solution on the surface of the weld metal formed by the welding torch part, and anatase type A structural material surface modification apparatus characterized by forming a titanium oxide layer. 前記チタン含有溶液はゾルゲル溶液であることを特徴とする請求項１記載の構造材の表面改質装置。   The surface modification apparatus for a structural material according to claim 1, wherein the titanium-containing solution is a sol-gel solution. 溶接トーチ部と溶射トーチ部とを有する構造材の表面改質装置において、
前記溶接トーチ部と溶射トーチ部を移動可能な連結部材により連結するとともに、前記溶射トーチ部は、前記溶接トーチ部で形成された溶接金属の表面にアナターゼ型酸化チタン粉末からなる溶射材をガスフレーム溶射により噴射しアナターゼ型酸化チタン層を形成することを特徴とする構造材の表面改質装置。 In the structural material surface modification apparatus having a welding torch part and a thermal spraying torch part,
The welding torch part and the thermal spraying torch part are connected by a movable connecting member, and the thermal spraying torch part is formed by applying a thermal spray material made of anatase-type titanium oxide powder on the surface of the weld metal formed by the welding torch part. An apparatus for surface modification of a structural material, wherein the anatase-type titanium oxide layer is formed by spraying. 前記溶接トーチ部はアーク溶接によって構造材に溶接金属を形成することを特徴とする請求項１乃至３いずれかに記載の構造材の表面改質装置。   4. The structural material surface reforming apparatus according to claim 1, wherein the welding torch part forms a weld metal on the structural material by arc welding. ガスシールドアーク溶接をおこなう溶接トーチ部とフィラーワイヤーとを有する構造材の表面改質装置において、
前記フィラーワイヤーにチタンを含有させ、シールドガスとして酸素とアルゴンの混合ガスを用いることにより溶接金属の表面にアナターゼ型酸化チタン層を形成することを特徴とする表面改質装置。 In a surface modification device for a structural material having a welding torch portion and a filler wire for performing gas shielded arc welding,
A surface modifying apparatus characterized in that an anatase-type titanium oxide layer is formed on the surface of a weld metal by containing titanium in the filler wire and using a mixed gas of oxygen and argon as a shielding gas . 前記溶接金属はニッケル基合金であることを特徴とする請求項１乃至５いずれかに記載の構造材の表面改質装置。   6. The structural material surface modification apparatus according to claim 1, wherein the weld metal is a nickel-based alloy. 請求項１乃至６記載の構造材の表面改質装置を用いて、構造材の溶接金属の表面にアナターゼ型酸化チタンからなる表面改質層を形成することを特徴とする構造材の表面改質方法。 Using a surface modifying apparatus structural member of claims 1 to 6, wherein the surface of the structural material and forming anatase titanium oxide emissions or Ranaru surface modification layer on the surface of the weld metal of the structural member Modification method.
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