JP2014122375A - Radiation shield coating member - Google Patents
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- JP2014122375A JP2014122375A JP2012278150A JP2012278150A JP2014122375A JP 2014122375 A JP2014122375 A JP 2014122375A JP 2012278150 A JP2012278150 A JP 2012278150A JP 2012278150 A JP2012278150 A JP 2012278150A JP 2014122375 A JP2014122375 A JP 2014122375A
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- 239000000843 powder Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明はγ線、Ｘ線、電子線を遮蔽するための放射線遮蔽コーティング部材に関し、特に放射線施設や、放射性廃棄物、核燃料、ラジオアイソトープ等の貯蔵容器、輸送容器、又は放射線関連機器を構成するのに適した放射線遮蔽コーティング部材に関するものである。 The present invention relates to a radiation shielding coating member for shielding γ-rays, X-rays, and electron beams, and particularly constitutes radiation facilities, storage containers such as radioactive waste, nuclear fuel, and radioisotopes, transport containers, or radiation-related equipment. The present invention relates to a radiation shielding coating member suitable for the above.
原子力発電所の事故により、セシウムなどの放射性物質で汚染されたガレキ、汚染水、汚泥、草木など放射性廃棄物の処理が問題となっている。そのため、放射性廃棄物の収集、運搬、更には長期貯蔵、中間貯蔵する放射性遮蔽特性に優れた容器等を構成する放射線遮蔽部材の開発が喫緊の課題となっている。 Due to an accident at a nuclear power plant, the disposal of radioactive waste such as rubble, contaminated water, sludge, and plants contaminated with radioactive materials such as cesium has become a problem. Therefore, it is an urgent issue to develop a radiation shielding member that constitutes a container and the like having excellent radioactive shielding characteristics for collecting and transporting radioactive waste, as well as for long-term storage and intermediate storage.
γ線、Ｘ線、電子線の遮蔽には一般的に、鉛、鉄、コンクリートなどが用いられている。例えばコンクリートを遮蔽部材として用いる場合、十分な遮蔽効果を得るために相当の壁厚を必要とし、容器の使用可能容積が小さくなるといった問題がある。またコンクリート構造体は、その吸水性により汚染水を吸水してしまう恐れもある。 Generally, lead, iron, concrete and the like are used for shielding γ rays, X rays and electron beams. For example, when concrete is used as a shielding member, there is a problem that a considerable wall thickness is required to obtain a sufficient shielding effect, and the usable volume of the container is reduced. Further, the concrete structure may absorb contaminated water due to its water absorption.
鉛、鉄、コンクリート等とポリエチレンやパラフィン等とを組み合わせた遮蔽部材も知られているが、ポリエチレンやパラフィンの接着性が悪く、製造及び施工が困難となる。更に、両者の熱膨張係数が著しく異なるために、温度差によって歪や反り、脱離が生じ、製造及び施工後の温度管理にかなりの注意を要する。また昨今の環境問題により、鉛に代表される人体に有害な材料は、可能な限り使用を控える傾向にある。 A shielding member in which lead, iron, concrete, etc., and polyethylene, paraffin or the like are combined is also known, but the adhesiveness of polyethylene or paraffin is poor, and manufacture and construction become difficult. Furthermore, since the thermal expansion coefficients of the two are significantly different, distortion, warpage, and detachment occur due to the temperature difference, and considerable care is required for temperature management after manufacturing and construction. In addition, due to recent environmental problems, materials harmful to the human body represented by lead tend to be avoided as much as possible.
例えば特許文献１には、中性子減速材と中性子吸収材とγ線遮蔽材からなる混合粉末を、鉄粉末に混合して成形した放射線遮蔽部材が記載されている。特許文献２には、放射線吸収率の高い材料と加硫ゴムとからなる放射線遮蔽材が記載されており、特許文献３には、樹脂中に、アンチモン、スズの金属単体粉末又は化合物粉末が配合された放射線遮蔽材が記載されている。 For example, Patent Document 1 describes a radiation shielding member formed by mixing a mixed powder composed of a neutron moderator, a neutron absorber, and a γ-ray shielding material with iron powder. Patent Document 2 describes a radiation shielding material composed of a material having a high radiation absorption rate and vulcanized rubber, and Patent Document 3 contains a simple metal powder or compound powder of antimony and tin in a resin. A radiation shielding material is described.
特許文献１のようにγ線遮蔽材を鉄粉末に混合した放射線遮蔽部材を用いて、例えば放射性廃棄物の容器を構成する場合、放射性廃棄物に含まれる汚染水等によって放射線遮蔽部材が腐食される。更に、汚染水等が放射線遮蔽部材を浸透していき、基材へ到達して当該基材を腐食させ、汚染水漏れを生じさせる。そのため、この放射線遮蔽部材は、放射性廃棄物を中間貯蔵で長期保管するための容器の構成部材には適さない。 For example, when a radioactive waste container is configured by using a radiation shielding member in which a γ-ray shielding material is mixed with iron powder as in Patent Document 1, the radiation shielding member is corroded by contaminated water or the like contained in the radioactive waste. The Furthermore, contaminated water or the like penetrates the radiation shielding member, reaches the base material, corrodes the base material, and causes contaminated water leakage. Therefore, this radiation shielding member is not suitable as a constituent member of a container for storing radioactive waste for a long time in intermediate storage.
特許文献２及び特許文献３のように、樹脂を多く配合した放射線遮蔽材の場合、γ線及びＸ線照射環境や水分環境では、分子鎖切断反応や架橋反応のため、比較的低線量照射で樹脂成分が劣化し、機械的強度や、耐食性、放射線遮蔽機能の低下などが懸念される。このため放射性廃棄物を中間貯蔵で長期保管するための容器の構成部材には適さない。 In the case of a radiation shielding material containing a large amount of resin, as in Patent Document 2 and Patent Document 3, in a gamma ray and X-ray irradiation environment or in a water environment, a relatively low dose irradiation is required due to molecular chain scission reaction or crosslinking reaction. The resin component is deteriorated, and there is a concern about mechanical strength, corrosion resistance, a decrease in radiation shielding function, and the like. For this reason, it is not suitable for the component of the container for storing radioactive waste for a long term by intermediate storage.
そこで本発明は、上記従来技術の問題点に鑑み、腐食が防止され、それと共にγ線又はＸ線の照射や水分環境によって、機械的強度、耐食性及び放射線遮蔽機能が低下しない放射線遮蔽コーティング部材を提供することを目的とする。 Therefore, in view of the above-mentioned problems of the prior art, the present invention provides a radiation shielding coating member that is prevented from being corroded, and that, together with the irradiation of gamma rays or X-rays or a moisture environment, the mechanical strength, corrosion resistance, and radiation shielding function are not deteriorated. The purpose is to provide.
上記目的を達成するため、次の技術的手段を講じた。
即ち本発明の放射線遮蔽コーティング部材は、基材と、前記基材の表面に形成された放射線遮蔽コーティングであって、Ｗ、Ｍｏのうち１種以上の元素を主成分とする材料よりなる放射線遮蔽コーティングと、前記放射線遮蔽コーティングの表面に形成された金属製の犠牲防食層であって、前記基材に対して低い標準電極電位を有する犠牲防食層とを備えることを特徴とする。
In order to achieve the above object, the following technical measures were taken.
That is, the radiation shielding coating member of the present invention is a radiation shielding coating formed on a substrate and a radiation shielding coating formed on the surface of the substrate, wherein the radiation shielding coating is made of a material mainly containing one or more elements of W and Mo. A sacrificial anticorrosion layer made of metal and formed on the surface of the radiation shielding coating, the sacrificial anticorrosion layer having a low standard electrode potential with respect to the substrate.
上記本発明の放射線遮蔽コーティング部材によれば、基材の表面に、Ｗ、Ｍｏのうち１種以上の元素を主成分とする材料よりなる放射線遮蔽コーティングが形成されているので、γ線又はＸ線の照射や水分環境によって放射線遮蔽コーティングが劣化せず、機械的強度、耐食性及び放射線遮蔽機能が低下しない。更に、放射線遮蔽コーティングの表面に、基材に対して低い標準電極電位を有する金属製の犠牲防食層が形成されている。そのため、汚染水等が仮に基材へ浸透した状態となっても、犠牲防食層の腐食が基材よりも先に進行し、基材の腐食を防止することができる。これらにより、高い耐久性を得ることができる。 According to the radiation shielding coating member of the present invention, the radiation shielding coating made of a material mainly composed of one or more elements of W and Mo is formed on the surface of the base material. The radiation shielding coating is not deteriorated by the irradiation of radiation and the moisture environment, and the mechanical strength, corrosion resistance and radiation shielding function are not lowered. Further, a metal sacrificial anticorrosive layer having a low standard electrode potential with respect to the substrate is formed on the surface of the radiation shielding coating. For this reason, even if contaminated water or the like is infiltrated into the base material, the sacrificial anticorrosion layer is corroded before the base material, thereby preventing the base material from being corroded. With these, high durability can be obtained.
前記犠牲防食層は、Ａｌ、Ｚｎ、Ｍｇ、Ｓｉから選択される元素単体、又はこれら元素の１種以上を主成分とする合金であることが好ましい。 The sacrificial anticorrosion layer is preferably an elemental element selected from Al, Zn, Mg, and Si, or an alloy containing at least one of these elements as a main component.
前記犠牲防食層を封孔剤によって封孔処理してもよく、この封孔剤として、Ｃｏ、Ｎｉ、Ｃｒ、Ａｌ、Ｚｎ、ＳｉＯ２、硅酸塩、リン酸塩、ゾルゲル剤、金属アルコキシド、シラン化合物の群から選択される１種以上の材料を含む封孔剤が挙げられる。更に、他の封孔剤として、高分子材料、パラフィン、防錆油、グリース、コールタールから選択される１種以上の材料を含む封孔剤が挙げられる。 The sacrificial anticorrosive layer may be sealed with a sealant, and as this sealant, Co, Ni, Cr, Al, Zn, SiO 2 , oxalate, phosphate, sol-gel agent, metal alkoxide, Examples thereof include a sealing agent containing one or more materials selected from the group of silane compounds. Furthermore, as another sealing agent, a sealing agent containing at least one material selected from a polymer material, paraffin, rust preventive oil, grease, and coal tar can be used.
犠牲防食層を、封孔剤によって封孔処理すれば、犠牲防食層を構成する皮膜層間の僅かな隙間が封孔剤によって埋められるか、又は犠牲防食層を構成する粒子周囲がコーティングされる。そのため、腐食環境におけるカソード面積を減少させることができ、基材の腐食の進行を遅らせることができる。これにより、耐久性を格段に向上させることができる。 When the sacrificial anticorrosive layer is sealed with a sealing agent, a slight gap between the coating layers constituting the sacrificial anticorrosive layer is filled with the sealing agent, or the particles surrounding the sacrificial anticorrosive layer are coated. Therefore, the cathode area in the corrosive environment can be reduced, and the progress of the corrosion of the substrate can be delayed. Thereby, durability can be improved markedly.
前記基材と前記放射線遮蔽コーティングとの間に、更に当該基材への水分の侵入を防ぐ防水層を備えることが好ましい。防水層の存在によって、基材への水分の侵入を防ぐことができれば、基材の腐食が生じず、放射線遮蔽コーティング部材の耐久性を更に向上させることができる。防水層を構成する材料の具体例として、Ｆｅ、Ａｌ、Ｔｉ、Ｎｉ、Ｃｒ、Ｚｎ、Ｃｏ、Ｙ、Ｐ、Ｍｏ、Ｗ、Ｓｉ、Ｍｎ、Ｖ、Ｎｂ、Ｂの群から選択される金属、又はこれらの組み合わせの合金よりなる材料が挙げられる。 It is preferable that a waterproof layer for preventing moisture from entering the base material is further provided between the base material and the radiation shielding coating. If moisture can be prevented from entering the substrate due to the presence of the waterproof layer, the substrate will not be corroded, and the durability of the radiation shielding coating member can be further improved. As a specific example of the material constituting the waterproof layer, Fe, Al, Ti, Ni, Cr, Zn, Co, Y, P, Mo, W, Si, Mn, V, Nb, a metal selected from the group of B, Or the material which consists of an alloy of these combination is mentioned.
前記放射線遮蔽コーティングが前記基材に対して高い標準電極電位を有している場合、腐食環境において、基材の腐食が放射線遮蔽コーティングよりも先に進行するおそれがある。このような場合に、犠牲防食層と基材との標準電極電位の電位差を、約０．１Ｖ以上としておけば、犠牲防食層の犠牲防食機能を十分に発揮させることができる。 If the radiation shielding coating has a high standard electrode potential relative to the substrate, the corrosion of the substrate may proceed before the radiation shielding coating in a corrosive environment. In such a case, if the potential difference between the standard electrode potentials of the sacrificial anticorrosive layer and the substrate is about 0.1 V or more, the sacrificial anticorrosive function of the sacrificial anticorrosive layer can be sufficiently exhibited.
前記放射線遮蔽コーティングの構成素材としては、例えばＷ−Ｍｏ合金、Ｗ−Ｎｉ合金、Ｗ−Ｃｕ合金、Ｗ−Ｆｅ合金、Ｍｏ−Ｗ合金、Ｍｏ−Ｎｉ合金、Ｍｏ−Ｃｕ合金、Ｍｏ−Ｆｅ合金、及びこれらを主体とする合金の何れかが挙げられる。 Examples of the constituent material of the radiation shielding coating include a W—Mo alloy, a W—Ni alloy, a W—Cu alloy, a W—Fe alloy, a Mo—W alloy, a Mo—Ni alloy, a Mo—Cu alloy, and a Mo—Fe alloy. , And alloys based on these.
前記放射線遮蔽コーティングの他の構成素材としては、ＷＢ、ＷＣ、Ｗ２Ｃ、ＭｏＢ、ＭｏＳｉ２、及びこれらを主体とする複合化合物の何れかを含む素材が挙げられる。 Examples of other constituent materials of the radiation shielding coating include materials including any of WB, WC, W 2 C, MoB, MoSi 2 , and composite compounds mainly composed of these.
前記基材は限定されず、例えばＦｅ、Ａｌ、Ｔｉ、Ｍｇ、Ｎｉ、及びこれらの合金、コンクリート、金属を含むセラミックス、炭素繊維を含むセラミックス、高分子材料、金属を含む高分子材料、炭素繊維を含む高分子材料の何れかが挙げられる。その中でも、比較的高い標準電極電位を有する金属を選択すれば、犠牲防食層を構成する素材の選択肢が広がり、コストを低減させることができる。 The base material is not limited. For example, Fe, Al, Ti, Mg, Ni, and alloys thereof, concrete, ceramics including metal, ceramics including carbon fiber, polymer material, polymer material including metal, and carbon fiber. Any of polymer materials containing Among these, if a metal having a relatively high standard electrode potential is selected, options for the material constituting the sacrificial anticorrosion layer are widened, and the cost can be reduced.
前記放射線遮蔽コーティングは、大気プラズマ溶射法、減圧プラズマ溶射法、高速フレーム溶射法、ガスフレーム溶射法、アーク溶射法、爆発溶射法、コールドスプレー法の何れかによって形成されていることが好ましい。このような方法を用いれば、優れた施工性が得られ、そのため現地施工が可能となり、かつ高品質の放射線遮蔽コーティング部材を得ることができる。 The radiation shielding coating is preferably formed by any one of an atmospheric plasma spraying method, a low pressure plasma spraying method, a high-speed flame spraying method, a gas flame spraying method, an arc spraying method, an explosion spraying method, and a cold spray method. By using such a method, excellent workability can be obtained, so that on-site construction can be performed, and a high-quality radiation shielding coating member can be obtained.
前記犠牲防食層は、大気プラズマ溶射法、減圧プラズマ溶射法、高速フレーム溶射法、ガスフレーム溶射法、アーク溶射法、爆発溶射法、コールドスプレー法、電気めっき法、溶融めっき法、化学気相蒸着（ＣＶＤ）法、物理気相蒸着（ＰＶＤ）法、塗装法の何れかによって形成されていることが好ましい。このような方法を用いれば、優れた施工性が得られ、そのため現地施工が可能となり、かつ高品質の放射線遮蔽コーティング部材を得ることができる。 The sacrificial anticorrosion layer is an atmospheric plasma spraying method, a low pressure plasma spraying method, a high-speed flame spraying method, a gas flame spraying method, an arc spraying method, an explosion spraying method, a cold spray method, an electroplating method, a hot dipping method, and a chemical vapor deposition method. It is preferably formed by any one of (CVD) method, physical vapor deposition (PVD) method, and coating method. By using such a method, excellent workability can be obtained, so that on-site construction can be performed, and a high-quality radiation shielding coating member can be obtained.
上記の通り本発明によれば、基材の表面に、Ｗ、Ｍｏのうち１種以上の元素を主成分とする材料よりなる放射線遮蔽コーティングが形成されているので、γ線又はＸ線の照射や水分環境によって放射線遮蔽コーティングが劣化せず、機械的強度、耐食性及び放射線遮蔽機能が低下しない。放射線遮蔽コーティングの表面に、犠牲防食層が形成されているため、犠牲防食層の腐食が基材よりも先に進行し、基材の腐食を防止することができる。これらにより、高い耐久性を得ることができる。 As described above, according to the present invention, since the radiation shielding coating made of a material mainly composed of one or more elements of W and Mo is formed on the surface of the substrate, irradiation with γ rays or X rays is performed. The radiation shielding coating is not deteriorated by the moisture environment, and the mechanical strength, corrosion resistance and radiation shielding function are not deteriorated. Since the sacrificial anticorrosive layer is formed on the surface of the radiation shielding coating, the corrosion of the sacrificial anticorrosive layer proceeds before the base material, and the base material can be prevented from corroding. With these, high durability can be obtained.
本発明の実施形態について説明する。図１は本発明の第１実施形態に係る放射線遮蔽コーティング部材の断面模式図である。本実施形態の放射線遮蔽コーティング部材１は、放射性廃棄物の収集、運搬、長期貯蔵、中間貯蔵用の容器を構成するためのものであり、基材２と、この基材２の表面２ａに形成された放射線遮蔽コーティング３と、放射線遮蔽コーティング３の表面３ａに形成された犠牲防食層４とを備えている。 An embodiment of the present invention will be described. FIG. 1 is a schematic cross-sectional view of a radiation shielding coating member according to the first embodiment of the present invention. The radiation shielding coating member 1 of this embodiment is for constituting a container for collection, transportation, long-term storage, and intermediate storage of radioactive waste, and is formed on the base 2 and the surface 2a of the base 2 And a sacrificial anticorrosion layer 4 formed on the surface 3 a of the radiation shielding coating 3.
放射線遮蔽コーティング３で被覆する基材２は限定されない。基材２の具体例として、例えば、Ｆｅ、Ａｌ、Ｔｉ、Ｍｇ、Ｎｉの金属単体、及びこれらの合金、コンクリート、金属を含むセラミックス、炭素繊維を含むセラミックス、高分子材料、金属を含む高分子材料、炭素繊維を含む高分子材料が挙げられる。 The base material 2 covered with the radiation shielding coating 3 is not limited. Specific examples of the base material 2 include, for example, simple metals such as Fe, Al, Ti, Mg, and Ni, and alloys thereof, concrete, ceramics containing metal, ceramics containing carbon fiber, polymer materials, and polymers containing metals. Examples of the material include polymer materials including carbon fibers.
本実施形態の基材２の厚みは約６ｍｍであり、放射線遮蔽コーティング３の厚みは約１ｍｍ、犠牲防食層４の厚みは約０．５ｍｍとなっているが、基材２、放射線遮蔽コーティング３及び犠牲防食層４の厚みは、放射線遮蔽コーティング部材１によって構成する構造体や放射性廃棄物などに応じて適宜変更される。 The thickness of the substrate 2 of this embodiment is about 6 mm, the thickness of the radiation shielding coating 3 is about 1 mm, and the thickness of the sacrificial anticorrosion layer 4 is about 0.5 mm. And the thickness of the sacrificial anticorrosion layer 4 is suitably changed according to the structure comprised by the radiation shielding coating member 1 or radioactive waste.
放射線遮蔽コーティング３を形成する材料は限定されず、例えばＷ（タングステン）材料に代表される、比重が１０〜２０g/cm3の高密度の金属材料が好適に用いられる。放射線遮蔽コーティング３を形成する材料として、Ｗ、Ｍｏ（モリブデン）のうち１種以上の元素を主成分とする材料や、Ｗ、Ｍｏのうち１種以上の元素を含む合金が好適である。上記の合金としては、Ｗ−Ｍｏ合金、Ｗ−Ｎｉ（ニッケル）合金、Ｗ−Ｃｕ（銅）合金、Ｗ−Ｆｅ（鉄）合金、Ｍｏ−Ｗ合金、Ｍｏ−Ｎｉ合金、Ｍｏ−Ｃｕ合金、Ｍｏ−Ｆｅ合金、及びこれらを主体とする合金が好適に用いられる。 The material for forming the radiation shielding coating 3 is not limited. For example, a high-density metal material having a specific gravity of 10 to 20 g / cm 3 , typically a W (tungsten) material, is preferably used. As a material for forming the radiation shielding coating 3, a material mainly containing one or more elements of W and Mo (molybdenum) and an alloy containing one or more elements of W and Mo are preferable. As said alloy, W-Mo alloy, W-Ni (nickel) alloy, W-Cu (copper) alloy, W-Fe (iron) alloy, Mo-W alloy, Mo-Ni alloy, Mo-Cu alloy, Mo—Fe alloys and alloys mainly composed of these are preferably used.
更に放射線遮蔽コーティング３を形成する材料として、ＷＢ、ＷＣ、Ｗ２Ｃ、ＭｏＢ、ＭｏＳｉ２、及びこれらを主体とする化合物が好適である。これらの材料は、単体で用いてもよく、バインダー材に配合して用いてもよい。その中でも、ＷＣ（タングステンカーバイド）系材料（例えばＷＣ系サーメット）が特に好適である。放射線遮蔽コーティング３は、Ｗ材料やＷＣ材料などの硬質材料が主成分となるので、放射線遮蔽コーティング部材１の表面硬度を高くすることができ、耐摩耗性を向上させることができる。 Furthermore, as a material for forming the radiation shielding coating 3, WB, WC, W 2 C, MoB, MoSi 2 and compounds mainly composed of these are suitable. These materials may be used alone or in combination with a binder material. Among these, WC (tungsten carbide) -based material (for example, WC-based cermet) is particularly suitable. Since the radiation shielding coating 3 is mainly composed of a hard material such as W material or WC material, the surface hardness of the radiation shielding coating member 1 can be increased, and the wear resistance can be improved.
バインダー材の具体例としては、例えばＣｏ、Ｎｉ、Ｃｒ、Ｆｅ、Ａｌ、Ｙ、Ｔｉ、Ｐ、Ｍｏ、Ｗ、Ｓｉ、Ｍｎ、Ｖ、Ｎｂ、Ｂの群から選択される元素単体、又はこれら元素の１種以上を主成分とする合金が挙げられる。より具体的には、ＭＣｒＡｌＹ、Ｃｒ−Ｎｉ、Ｃｏ−Ｃｒ、ハステロイ合金、Ｎｉ−Ｐが挙げられる。放射線遮蔽コーティング３にこれらバインダー材を用いた場合、バインダー材とＷＣなどの硬質粒子の作用によって、耐摩耗性を更に向上させることができる。 Specific examples of the binder material include, for example, elemental elements selected from the group of Co, Ni, Cr, Fe, Al, Y, Ti, P, Mo, W, Si, Mn, V, Nb, and B, or these elements An alloy containing one or more of these as a main component can be given. More specifically, MCrAlY, Cr—Ni, Co—Cr, Hastelloy alloy, and Ni—P may be mentioned. When these binder materials are used for the radiation shielding coating 3, the wear resistance can be further improved by the action of the binder material and hard particles such as WC.
放射線遮蔽効果に関し、Ｗ（比重：１８．５g/cm3）及びＷＣ系サーメット（比重：１１．３g/cm3）で、鉛以上のγ線遮蔽能力を示す。例えばＷ材料からなる放射線遮蔽コーティング３（膜厚：２mm）のγ線遮蔽効果は、同じ厚みの鉛板の１．４倍、鋼板の２．２倍、コンクリートの９倍を示す。 With regard to the radiation shielding effect, W (specific gravity: 18.5 g / cm 3 ) and WC cermet (specific gravity: 11.3 g / cm 3 ) exhibit γ-ray shielding ability higher than that of lead. For example, the gamma ray shielding effect of the radiation shielding coating 3 (film thickness: 2 mm) made of W material is 1.4 times that of a lead plate having the same thickness, 2.2 times that of a steel plate, and 9 times that of concrete.
放射線遮蔽コーティング３は、大気プラズマ溶射法、減圧プラズマ溶射法、高速フレーム溶射法、ガスフレーム溶射法、アーク溶射法、爆発溶射法、コールドスプレー法のいずれかの方法で形成されている。 The radiation shielding coating 3 is formed by any one of atmospheric plasma spraying, reduced pressure plasma spraying, high-speed flame spraying, gas flame spraying, arc spraying, explosion spraying, and cold spraying.
これら溶射法又はコールドスプレー法を用いることによって、耐久性に優れ、かつ高品質の放射線遮蔽コーティング３を得ることができる。また、係る方法を用いれば、優れた施工性が得られ、そのため現地施工が可能となる。一般的なスプレー塗布などによって放射線遮蔽コーティング３を形成してもよい。各溶射法及びコールドスプレー法による成膜条件は、基材、原料粉末、膜厚、製造環境などに応じて適宜設定すればよい。 By using these thermal spraying methods or cold spray methods, the radiation shielding coating 3 having excellent durability and high quality can be obtained. Moreover, if such a method is used, excellent workability can be obtained, so that on-site construction is possible. The radiation shielding coating 3 may be formed by general spray application or the like. The film forming conditions by each thermal spraying method and cold spray method may be appropriately set according to the substrate, raw material powder, film thickness, manufacturing environment, and the like.
Ｗ材料からなる放射線遮蔽コーティング３を、大気プラズマ溶射法で溶射する場合の条件と、ＷＣ−ＣｒＮｉ材料からなる放射線遮蔽コーティング３を、高速フレーム溶射法で溶射する場合の条件を以下に示す。なお、以下の条件は一例であって溶射条件は適宜設定される。 The conditions for spraying the radiation shielding coating 3 made of the W material by the atmospheric plasma spraying method and the conditions for spraying the radiation shielding coating 3 made of the WC-CrNi material by the high-speed flame spraying method are shown below. In addition, the following conditions are an example and spraying conditions are set suitably.
Ｗ（大気プラズマ溶射法）
溶射装置：Ｓｕｌｚｅｒ Ｍｅｔｃｏ−Ｆ４
ノズル：φ６ｍｍ
アルゴンガス流量：５０ＮＬＰＭ
水素ガス流量：１０ＮＬＰＭ
トーチ入力：４０ｋＷ
溶射距離：１５０ｍｍ
W (Atmospheric plasma spraying method)
Thermal spray equipment: Sulzer Metco-F4
Nozzle: φ6mm
Argon gas flow rate: 50NLPM
Hydrogen gas flow rate: 10NLPM
Torch input: 40kW
Thermal spray distance: 150mm
ＷＣ−ＣｒＮｉ（高速フレーム溶射法）
溶射装置：ＴＡＦＡ−ＪＰ５０００
バレル長さ：８ｉｎｃｈ
酸素流量：２０００ｓｃｆｈ
灯油流量：６．０ｇｐｈ
溶射距離：４００ｍｍ
WC-CrNi (High-speed flame spraying method)
Thermal spraying equipment: TAFA-JP5000
Barrel length: 8 inch
Oxygen flow rate: 2000 scfh
Kerosene flow rate: 6.0gph
Thermal spraying distance: 400mm
放射線遮蔽コーティング３の表面３ａに形成された犠牲防食層４は金属の素材からなる。犠牲防食層４は、大気プラズマ溶射法、減圧プラズマ溶射法、高速フレーム溶射法、ガスフレーム溶射法、アーク溶射法、爆発溶射法、コールドスプレー法、電気めっき法、溶融めっき法、化学気相蒸着（ＣＶＤ）法、物理気相蒸着（ＰＶＤ）法、塗装法の何れかの方法で形成されている。これら溶射法等を用いることによって、耐久性に優れ、かつ高品質の犠牲防食層４を得ることができる。また、係る方法を用いれば、優れた施工性が得られ、そのため現地施工が可能となる。一般的なスプレー塗布などによって犠牲防食層４を形成してもよい。各成膜条件は、基材、原料粉末、膜厚、製造環境などに応じて適宜設定すればよい。 The sacrificial anticorrosion layer 4 formed on the surface 3a of the radiation shielding coating 3 is made of a metal material. The sacrificial anticorrosion layer 4 is formed by atmospheric plasma spraying, reduced pressure plasma spraying, high-speed flame spraying, gas flame spraying, arc spraying, explosion spraying, cold spraying, electroplating, hot dipping, chemical vapor deposition. It is formed by any one of (CVD) method, physical vapor deposition (PVD) method, and coating method. By using these thermal spraying methods and the like, the sacrificial anticorrosive layer 4 having excellent durability and high quality can be obtained. Moreover, if such a method is used, excellent workability can be obtained, so that on-site construction is possible. The sacrificial anticorrosive layer 4 may be formed by general spray coating or the like. Each film forming condition may be appropriately set according to the base material, raw material powder, film thickness, manufacturing environment, and the like.
犠牲防食層４を構成する金属は限定しないが、基材２に対して低い標準電極電位を有する金属であり、好ましくは標準電極電位が−２．５〜＋１．０Ｖであり、より好ましくは−２．５〜０Ｖである。標準電極電位が低すぎると、不安定となり、高すぎると加工性、生産性が低下するおそれがある。ここで、標準電極電位とは、金属をその金属イオンを含む溶液中に浸した際の電極電位と、標準水素電極（１気圧で水素ガスと接触している１規定のＨＣｌ溶液に浸した白金よりなる電極）電位との差で表される。例えばＭｇ：約−２．３４Ｖ、Ａｌ：−１．６７Ｖ、Ｚｎ：−０．７６Ｖ、Ｃｒ：−０．７１Ｖ、Ｆｅ：−０．４４、Ｎｉ：−０．２５等である。 The metal constituting the sacrificial anticorrosion layer 4 is not limited, but is a metal having a low standard electrode potential with respect to the substrate 2, preferably the standard electrode potential is −2.5 to +1.0 V, more preferably − 2.5 to 0V. If the standard electrode potential is too low, it becomes unstable, and if it is too high, workability and productivity may be reduced. Here, the standard electrode potential refers to the electrode potential when a metal is immersed in a solution containing the metal ions and the standard hydrogen electrode (platinum immersed in a 1N HCl solution in contact with hydrogen gas at 1 atm. Electrode) expressed as a difference from the potential. For example, Mg: about -2.34 V, Al: -1.67 V, Zn: -0.76 V, Cr: -0.71 V, Fe: -0.44, Ni: -0.25.
犠牲防食層４を構成する金属の具体例として、Ａｌ、Ｚｎ、Ｍｇ、Ｓｉから選択される元素単体、又はこれら元素の１種以上を主成分とする合金が挙げられる。犠牲防食層４の合金の種類としては、Ａｌ−Ｚｎ、Ａｌ−Ｍｇ、Ａｌ−Ｓｉ、Ａｌ−Ｚｎ−Ｍｇ、Ａｌ−Ｚｎ−Ｓｉ、Ａｌ−Ｍｇ−Ｓｉ、Ｚｎ−Ｍｇ、Ｚｎ−Ｓｉが好ましい。その中でもＭｇ元素を添加した合金は、犠牲防食層４に環境気体との反応による表面不動態皮膜が生じ難くなるので、犠牲防食層４が良好な犠牲防食機能を維持し続けることができる。 Specific examples of the metal constituting the sacrificial anticorrosion layer 4 include a single element selected from Al, Zn, Mg, and Si, or an alloy containing at least one of these elements as a main component. As the alloy type of the sacrificial anticorrosion layer 4, Al—Zn, Al—Mg, Al—Si, Al—Zn—Mg, Al—Zn—Si, Al—Mg—Si, Zn—Mg, and Zn—Si are preferable. . Among them, the alloy to which Mg element is added makes it difficult for a surface passive film to be formed on the sacrificial anticorrosive layer 4 due to the reaction with the environmental gas, so that the sacrificial anticorrosive layer 4 can continue to maintain a good sacrificial anticorrosive function.
犠牲防食層４に、基材２に対して低い標準電極電位を有する金属を選択するのは、基材２を腐食させないためである。犠牲防食層４が基材２に対して低い標準電極電位を有する金属であれば、汚染水等が浸透してきた腐食環境において、基材２よりも先に犠牲防食層４が腐食される。そのため、基材２の腐食の進行を遅らせることができる。 The reason why the metal having a low standard electrode potential with respect to the base material 2 is selected for the sacrificial anticorrosion layer 4 is that the base material 2 is not corroded. If the sacrificial anticorrosion layer 4 is a metal having a low standard electrode potential with respect to the base material 2, the sacrificial anticorrosion layer 4 is corroded prior to the base material 2 in a corrosive environment where contaminated water or the like has permeated. Therefore, the progress of the corrosion of the base material 2 can be delayed.
仮に基材２にＳＳ４００鋼、放射線遮蔽コーティング３にＷ材料を用いた場合、放射線遮蔽コーティング３が基材２に対して高い標準電極電位を有することになり、放射線遮蔽コーティング３と基材２の関係では、腐食環境において基材２の腐食が優先される。この場合、犠牲防食層４と基材２との標準電極電位の電位差が約０．１Ｖ以上であることが好ましく、より好ましくは約０．３Ｖ以上であり、最も好ましくは約０．５Ｖ以上である。 If SS400 steel is used for the base material 2 and W material is used for the radiation shielding coating 3, the radiation shielding coating 3 has a high standard electrode potential with respect to the base material 2. In relation, the corrosion of the substrate 2 is prioritized in a corrosive environment. In this case, the standard electrode potential difference between the sacrificial anticorrosive layer 4 and the substrate 2 is preferably about 0.1 V or more, more preferably about 0.3 V or more, and most preferably about 0.5 V or more. is there.
犠牲防食層４が基材２に対して低い標準電極電位を有し、犠牲防食層４の基材２に対する標準電極電位の電位差が約０．１Ｖ以上であれば、犠牲防食層４が基材２に対してより優先的に腐食される。そのため、基材２が放射線遮蔽コーティング３より腐食され易い場合であっても、犠牲防食層４の犠牲防食機能を十分に発揮させることができ、基材２に対する良好な腐食抑制効果を得ることができる。 If the sacrificial anticorrosive layer 4 has a low standard electrode potential with respect to the base material 2 and the potential difference of the standard electrode potential of the sacrificial anticorrosive layer 4 with respect to the base material 2 is about 0.1 V or more, the sacrificial anticorrosive layer 4 is the base material. 2 is preferentially corroded. Therefore, even if the base material 2 is more easily corroded than the radiation shielding coating 3, the sacrificial anticorrosion function of the sacrificial anticorrosion layer 4 can be sufficiently exerted, and a good corrosion inhibiting effect on the base material 2 can be obtained. it can.
基材２の種類は上記のとおり限定しないが、比較的高い標準電極電位を有する金属を選択すれば、犠牲防食層４を構成する素材の選択肢が広がり、コストを低減させることができる。 Although the kind of the base material 2 is not limited as described above, if a metal having a relatively high standard electrode potential is selected, choices of materials constituting the sacrificial anticorrosion layer 4 are widened, and costs can be reduced.
本実施形態の犠牲防食層４は封孔剤によって封孔処理されている。封孔処理の方法としては、はけ塗り、ディッピング、スプレー、ローラー塗布等、従来の方法が用いられる。犠牲防食層４を封孔剤によって封孔処理すれば、犠牲防食層４を構成する皮膜層間の僅かな気孔や割れによる隙間が封孔剤によって埋められる。また、犠牲防食層４を構成する各々の粒子周囲がコーティングされる。そのため、腐食環境におけるカソード面積を減少させることができ、基材２の腐食の進行を遅らせることができる。更に水分が侵入し難くなり、水分環境による基材２の劣化をも抑えることができる。これにより、耐久性を格段に向上させることができる。 The sacrificial anticorrosive layer 4 of this embodiment is sealed with a sealing agent. As a sealing treatment method, conventional methods such as brush coating, dipping, spraying, and roller coating are used. If the sacrificial anticorrosive layer 4 is sealed with a sealing agent, slight pores or cracks between the coating layers constituting the sacrificial anticorrosive layer 4 are filled with the sealing agent. Further, the periphery of each particle constituting the sacrificial anticorrosive layer 4 is coated. Therefore, the cathode area in the corrosive environment can be reduced, and the progress of the corrosion of the base material 2 can be delayed. Furthermore, it becomes difficult for moisture to enter, and deterioration of the substrate 2 due to moisture environment can be suppressed. Thereby, durability can be improved markedly.
なお、封孔剤は犠牲防食層４だけでなく、放射線遮蔽コーティング３にも侵入していることがより好ましい。封孔剤が、放射線遮蔽コーティング３にまで到達していれば、耐久性を更に向上させることができるからである。 It is more preferable that the sealant penetrates not only the sacrificial anticorrosive layer 4 but also the radiation shielding coating 3. This is because the durability can be further improved if the sealing agent reaches the radiation shielding coating 3.
封孔剤の具体例として、Ｃｏ、Ｎｉ、Ｃｒ、Ａｌ、Ｚｎ、ＳｉＯ２、硅酸塩、リン酸塩、ゾルゲル剤、金属アルコキシド、シラン化合物、高分子材料、パラフィン、防錆油、グリース、コールタールの群から選択される１種以上の材料を含む材料が挙げられる。高分子の封孔剤として、ビニル樹脂、エポキシ樹脂、ウレタン樹脂、アクリル樹脂、フェノール樹脂などを用いることができるが、好ましくは無機系材料である。放射線照射環境における長期使用の観点から、高分子材料でない材料の方が劣化を無くすことができ、長期使用に耐えるからである。封孔剤としては、無機材料のみ、無機材料を主成分として有機材料を混合したものが好適である。 Specific examples of the sealant include Co, Ni, Cr, Al, Zn, SiO 2 , oxalate, phosphate, sol-gel agent, metal alkoxide, silane compound, polymer material, paraffin, rust preventive oil, grease, Examples include materials containing one or more materials selected from the group of coal tar. As the polymer sealing agent, a vinyl resin, an epoxy resin, a urethane resin, an acrylic resin, a phenol resin, or the like can be used, and an inorganic material is preferable. This is because, from the viewpoint of long-term use in a radiation irradiation environment, a material that is not a polymer material can eliminate deterioration and endure long-term use. As the sealing agent, only an inorganic material or a mixture of an inorganic material as a main component and an organic material is suitable.
基材２と放射線遮蔽コーティング３との間にボンドコートを設けてもよい。ボンドコートとしては、Ｆｅ、Ａｌ、Ｔｉ、Ｎｉ、Ｃｒ、Ｚｎ、Ｃｏ、Ｙから選択される金属、又はこれら組み合わせの合金が好ましい。基材２と放射線遮蔽コーティング３との間にボンドコートを設ければ、放射線遮蔽コーティング３が基材２から脱離し難くなり、放射線遮蔽コーティング部材１の密着性を向上させることができる。 A bond coat may be provided between the substrate 2 and the radiation shielding coating 3. As the bond coat, a metal selected from Fe, Al, Ti, Ni, Cr, Zn, Co, and Y, or an alloy of these combinations is preferable. If a bond coat is provided between the base material 2 and the radiation shielding coating 3, the radiation shielding coating 3 becomes difficult to be detached from the base material 2, and the adhesion of the radiation shielding coating member 1 can be improved.
例えば、基材２をＳＳ４００鋼とし、その表面２ａにＷ材料からなる放射線遮蔽コーティング３を形成した場合の密着力は、所定の試験条件下で５ＭＰａを示す。これに対し、基材２をＳＳ４００鋼とし、その表面２ａにボンドコートとしてＡｌボンドコートを塗布し、塗布した表面にＷ材料からなる放射線遮蔽コーティング３を形成した場合の密着力は、同じ試験条件下で１０ＭＰａを示す。このようにボンドコートを介在させた場合、基材２と放射線遮蔽コーティング３との密着力が格段に向上する。 For example, when the base material 2 is SS400 steel and the radiation shielding coating 3 made of the W material is formed on the surface 2a thereof, the adhesion force is 5 MPa under predetermined test conditions. In contrast, when the base material 2 is SS400 steel, an Al bond coat is applied to the surface 2a as a bond coat, and the radiation shielding coating 3 made of the W material is formed on the applied surface, the adhesion strength is the same test condition. 10 MPa is shown below. When the bond coat is interposed as described above, the adhesion between the base material 2 and the radiation shielding coating 3 is remarkably improved.
本実施形態の放射線遮蔽コーティング部材１によれば、基材２の表面２ａに、例えばＷ、Ｍｏのうち１種以上の元素を主成分とする材料よりなる放射線遮蔽コーティング３が形成されているので、γ線又はＸ線の照射や水分環境によって放射線遮蔽コーティング３が劣化せず、機械的強度、耐食性及び放射線遮蔽機能が低下しない。更に、放射線遮蔽コーティング３の表面３ａに、基材２に対して低い標準電極電位を有する金属製の犠牲防食層４が形成されている。そのため、汚染水等が仮に基材２へ浸透した状態となっても、犠牲防食層４の腐食が基材よりも先に進行し、基材２の腐食を防止することができる。これらにより、γ線又はＸ線の照射や水分環境において高い耐久性を得ることができる。放射線遮蔽コーティング３は、Ｗ材料やＷＣ材料などの硬質材料が主成分となるので、表面硬度が高くなり、耐摩耗性をも向上させることができる。 According to the radiation shielding coating member 1 of the present embodiment, the radiation shielding coating 3 made of a material mainly composed of one or more elements of W and Mo, for example, is formed on the surface 2a of the substrate 2. The radiation shielding coating 3 is not deteriorated by irradiation with γ rays or X rays or a moisture environment, and the mechanical strength, corrosion resistance and radiation shielding function are not lowered. Furthermore, a sacrificial anticorrosive layer 4 made of metal having a low standard electrode potential with respect to the substrate 2 is formed on the surface 3 a of the radiation shielding coating 3. Therefore, even if contaminated water or the like is in a state of permeating into the base material 2, the sacrificial anticorrosive layer 4 is corroded before the base material, and the base material 2 can be prevented from corroding. As a result, high durability can be obtained in irradiation with γ rays or X rays or in a moisture environment. Since the radiation shielding coating 3 is mainly composed of a hard material such as a W material or a WC material, the surface hardness is increased and the wear resistance can be improved.
放射線遮蔽コーティング３及び犠牲防食層４は、上記の各種溶射法などで形成されるため、層及び皮膜厚さ：０．０１ｍｍから数１０ｍｍの範囲で自由に選択可能であり、容易に施工可能である。このような優れた施工性から、工場のみならず現地施工によって、放射線遮蔽コーティング３及び犠牲防食層４を、基材２の表面２ａへ形成することができる。円筒構造物の内面や、複雑な形状の構造物など、いかなる形状の構造物にも、放射線遮蔽コーティング３及び犠牲防食層４の形成が可能である。そのため、従来では被覆できなかった箇所への放射線遮蔽コーティング３及び犠牲防食層４の形成が可能となり、ひいてはセシウムなどの放射性物質で汚染されたガレキ、汚染水、汚泥、草木など放射性廃棄物の処理を効率良く進めることができる。更に柔軟性に優れたミクロな層構造の放射線遮蔽コーティング３及び犠牲防食層４が得られ、高品質の放射線遮蔽コーティング部材１を得ることができる。放射線遮蔽コーティング３が、Ｗ、ＷＣ系材料など上記各種の材料で形成されていることにより、人体に悪影響を及ぼすことが殆どなく、安全性が高い。 Since the radiation shielding coating 3 and the sacrificial anticorrosion layer 4 are formed by the above-described various thermal spraying methods, the layer and coating thickness can be freely selected within a range of 0.01 mm to several tens of mm, and can be easily constructed. is there. From such excellent workability, the radiation shielding coating 3 and the sacrificial anticorrosion layer 4 can be formed on the surface 2a of the base material 2 not only by the factory but also by local construction. The radiation shielding coating 3 and the sacrificial anticorrosion layer 4 can be formed on a structure having any shape such as an inner surface of a cylindrical structure or a structure having a complicated shape. Therefore, it is possible to form the radiation shielding coating 3 and the sacrificial anticorrosion layer 4 in the places that could not be covered conventionally, and as a result, the treatment of radioactive waste such as rubble, contaminated water, sludge, and vegetation contaminated with radioactive materials such as cesium. Can be carried out efficiently. Furthermore, the radiation shielding coating 3 and the sacrificial anticorrosive layer 4 having a micro layer structure excellent in flexibility can be obtained, and a high quality radiation shielding coating member 1 can be obtained. Since the radiation shielding coating 3 is formed of the above-described various materials such as W and WC materials, the human body is hardly adversely affected and safety is high.
犠牲防食層４による犠牲防食機能に、封孔剤などによる二次的防食機能が備わった重防食によって、基材２の腐食が高度なレベルで防止されている。これにより、放射線遮蔽コーティング部材１で構成された構造物の長期に渡る耐久性、及び高い放射線レベルでの環境における耐腐食性を格段に向上させることができる。 Corrosion of the base material 2 is prevented at a high level by the heavy anticorrosion provided with the secondary anticorrosion function such as a sealing agent in addition to the sacrificial anticorrosion function by the sacrificial anticorrosion layer 4. Thereby, durability over the long term of the structure comprised with the radiation shielding coating member 1, and the corrosion resistance in the environment in a high radiation level can be improved significantly.
図２は本発明の第２実施形態に係る放射線遮蔽コーティング部材の断面模式図である。本実施形態では、基材１１と放射線遮蔽コーティング１３との間に、更に基材１１への水分の侵入を防ぐ防水層１２を設けている。基材１１、放射線遮蔽コーティング１３、犠牲防食層１４及び封孔剤による封孔処理は第１実施形態と共通している。防水層１２は、大気プラズマ溶射法、減圧プラズマ溶射法、高速フレーム溶射法、ガスフレーム溶射法、アーク溶射法、爆発溶射法、コールドスプレー法のいずれかの方法で形成された皮膜である。防水層１２に用いられる素材の具体例としては、Ｆｅ、Ａｌ、Ｔｉ、Ｎｉ、Ｃｒ、Ｚｎ、Ｃｏ、Ｙ、Ｐ、Ｍｏ、Ｗ、Ｓｉ、Ｍｎ、Ｖ、Ｎｂ、Ｂの群から選択される金属、又はこれらの組み合わせの合金が挙げられる。より具体的には、ＭＣｒＡｌＹ、Ｃｒ−Ｎｉ、Ｃｏ−Ｃｒ、ハステロイ合金、Ｎｉ−Ｐが挙げられる FIG. 2 is a schematic cross-sectional view of a radiation shielding coating member according to the second embodiment of the present invention. In the present embodiment, a waterproof layer 12 for preventing moisture from entering the base material 11 is further provided between the base material 11 and the radiation shielding coating 13. The sealing process using the base material 11, the radiation shielding coating 13, the sacrificial anticorrosive layer 14, and the sealing agent is the same as that in the first embodiment. The waterproof layer 12 is a film formed by any one of the atmospheric plasma spraying method, the low pressure plasma spraying method, the high-speed flame spraying method, the gas flame spraying method, the arc spraying method, the explosion spraying method, and the cold spray method. Specific examples of the material used for the waterproof layer 12 are selected from the group of Fe, Al, Ti, Ni, Cr, Zn, Co, Y, P, Mo, W, Si, Mn, V, Nb, and B. A metal or an alloy of a combination thereof can be given. More specifically, MCrAlY, Cr—Ni, Co—Cr, Hastelloy alloy, Ni—P may be mentioned.
防水層１２の存在によって、基材１１への水分の侵入を防ぐことができる。従って、犠牲防食層４による犠牲防食機能に、封孔剤及び防水層１２などによる二次的防食機能が備わった重防食によって、基材２の腐食速度を更に遅らせることができる。これにより、放射線遮蔽コーティング部材１０で構成された構造物の長期に渡る耐久性、及び高い放射線レベルでの環境における耐腐食性を格段に向上させることができる。 The presence of the waterproof layer 12 can prevent moisture from entering the base material 11. Therefore, the corrosion rate of the substrate 2 can be further delayed by the heavy corrosion protection provided with the sacrificial anticorrosion function by the sacrificial anticorrosion layer 4 and the secondary anticorrosion function by the sealing agent and the waterproof layer 12. Thereby, durability over the long term of the structure comprised with the radiation shielding coating member 10, and the corrosion resistance in the environment in a high radiation level can be improved significantly.
以下、実施例により本発明をより詳細に説明するが、本発明は以下の実施例に限定されるものではない。本発明に係る実施例及び比較例の試料を製作し、ＪＩＳＺ２３７１に準拠した塩水噴霧試験を実施し、表面観察及びＳＥＭ写真による断面観察を行った。塩水噴霧試験は塩水噴霧試験機（ＳＴ−ＩＳＯ−３型）、噴霧塔方式、スガ試験機（株）製で行った。試験前、２４時間後、４８時間後、７２時間後及び９６時間後の各試験片の表面を観察し、発錆の状態等から耐水性及び耐食性の優劣を判定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example. Samples of examples and comparative examples according to the present invention were manufactured, a salt spray test based on JISZ2371 was performed, and surface observation and cross-sectional observation by SEM photographs were performed. The salt spray test was conducted with a salt spray tester (ST-ISO-3 type), a spray tower system, and Suga Test Instruments Co., Ltd. Before the test, 24 hours, 48 hours, 72 hours, and 96 hours, the surface of each test piece was observed, and the superiority or inferiority of water resistance and corrosion resistance was determined from the state of rusting.
塩水噴霧試験の試験条件は下記のとおりである。
噴霧採取液塩濃度：４５±５ｇ／ｌ
噴霧採取ＰＨ：６．５〜７．２
供給空気圧力：０．０９８±０．０１０ＭＰａ
塩水噴霧量：１．５±０．５ｍｌ／ｈ・８０ｃｍ２
空気飽和器温度：４７±２℃
塩水層温度：３５±２℃
試験室温度：３５±２℃
試験片支持：２０±５°
観察時期：試験前、２４時間後、４８時間後、７２時間後、９６時間後
The test conditions of the salt spray test are as follows.
Spray collected liquid salt concentration: 45 ± 5 g / l
Spray sampling PH: 6.5-7.2
Supply air pressure: 0.098 ± 0.010 MPa
Salt spray amount: 1.5 ± 0.5 ml / h · 80 cm 2
Air saturator temperature: 47 ± 2 ° C
Brine temperature: 35 ± 2 ° C
Test room temperature: 35 ± 2 ° C
Test piece support: 20 ± 5 °
Observation period: Before test, 24 hours, 48 hours, 72 hours, 96 hours
実施例１〜３として、５０×５０×６ｍｍのＳＳ４００鋼の片面に、大気プラズマ溶射法を用いて上記成膜条件でＷ皮膜（放射線遮蔽コーティング）を形成し、その表面にＡｌ皮膜（犠牲防食層）を形成した。実施例２及び３には封孔処理を行った。実施例４〜７として、５０×５０×６ｍｍのＳＳ４００鋼の片面に、大気プラズマ溶射法を用いてＮｉ−Ｃｒ（防水層）を形成し、その表面に大気プラズマ溶射法を用いてＷ皮膜（放射線遮蔽コーティング）を形成し、その表面にＡｌ皮膜（犠牲防食層）を形成した。実施例５〜７には封孔処理を行った。Ｗ皮膜の膜厚は５００μｍとし、Ａｌ皮膜の膜厚は１００μｍとし、Ｎｉ−Ｃｒの膜厚は１００μｍとした。実施例１〜７の防水層、封孔処理の有り無し、材料、封孔処理回数を表１に示す。封孔処理の塗布１回とは、塗布→焼成を１回行ったことを表す。 As Examples 1 to 3, a W film (radiation shielding coating) is formed on one surface of 50 × 50 × 6 mm SS400 steel using the atmospheric plasma spraying method under the above film formation conditions, and an Al film (sacrificial corrosion protection) is formed on the surface. Layer). Examples 2 and 3 were sealed. As Examples 4 to 7, Ni—Cr (waterproof layer) is formed on one surface of 50 × 50 × 6 mm SS400 steel using an atmospheric plasma spraying method, and a W coating (atmospheric plasma spraying method is used on the surface). (Radiation shielding coating) was formed, and an Al film (sacrificial anticorrosive layer) was formed on the surface. Examples 5-7 were subjected to sealing treatment. The film thickness of the W film was 500 μm, the film thickness of the Al film was 100 μm, and the film thickness of Ni—Cr was 100 μm. Table 1 shows the waterproof layers of Examples 1 to 7, presence or absence of sealing treatment, materials, and the number of sealing treatments. One application of the sealing treatment means that application → firing is performed once.
比較例１〜５として、５０×５０×６ｍｍのＳＳ４００鋼の片面に、大気プラズマ溶射法を用いて上記成膜条件でＷ皮膜（放射線遮蔽コーティング）を形成した。その後、比較例１を除く試験片に封孔処理を行った。比較例６〜８として、５０×５０×６ｍｍのＳＳ４００鋼の片面に、大気プラズマ溶射法を用いてＮｉ−Ｃｒ（防水層）を形成し、その表面に大気プラズマ溶射法を用いてＷ皮膜（放射線遮蔽コーティング）を形成した。その後、比較例６を除く試験片に封孔処理を行った。Ｗ皮膜の膜厚は５００μｍとし、Ｎｉ−Ｃｒの膜厚は１００μｍとした。比較例１〜８の防水層、犠牲防食層、封孔処理の有り無し、材料、封孔処理の回数を表２に示す。封孔処理の塗布１回とは、塗布→焼成を１回行ったことを表す。 As Comparative Examples 1 to 5, a W film (radiation shielding coating) was formed on one surface of 50 × 50 × 6 mm SS400 steel using the atmospheric plasma spraying method under the above film forming conditions. Thereafter, the test piece except Comparative Example 1 was subjected to sealing treatment. As Comparative Examples 6 to 8, Ni—Cr (waterproof layer) is formed on one surface of 50 × 50 × 6 mm SS400 steel using an atmospheric plasma spraying method, and a W coating (atmospheric plasma spraying method is used on the surface). Radiation shielding coating) was formed. Thereafter, the test piece excluding Comparative Example 6 was subjected to sealing treatment. The film thickness of the W film was 500 μm, and the film thickness of Ni—Cr was 100 μm. Table 2 shows the waterproof layer, sacrificial anticorrosive layer, presence / absence of sealing treatment, material, and number of sealing treatments of Comparative Examples 1 to 8. One application of the sealing treatment means that application → firing is performed once.
図３は実施例１〜３の塩水噴霧試験後の表面写真であり、図４は実施例１〜３の塩水噴霧試験後の断面ＳＥＭ写真である。図５は実施例４〜７の塩水噴霧試験後の表面写真である。図６は比較例１〜５の塩水噴霧試験後の表面写真であり、図７は比較例１、３、４の塩水噴霧試験後の断面ＳＥＭ写真である。図８は比較例６、７、８の塩水噴霧試験後の表面写真であり、図９は比較例６、７、８の塩水噴霧試験後の断面ＳＥＭ写真である。 FIG. 3 is a surface photograph after the salt spray test of Examples 1 to 3, and FIG. 4 is a cross-sectional SEM photograph after the salt spray test of Examples 1 to 3. FIG. 5 is a surface photograph after the salt spray test of Examples 4 to 7. 6 is a surface photograph after the salt spray test of Comparative Examples 1 to 5, and FIG. 7 is a cross-sectional SEM photograph after the salt spray test of Comparative Examples 1, 3, and 4. FIG. 8 is a surface photograph after the salt spray test of Comparative Examples 6, 7, and 8, and FIG. 9 is a cross-sectional SEM photograph after the salt spray test of Comparative Examples 6, 7, and 8.
実施例１〜３で赤錆無し、Ａｌ皮膜の犠牲防食作用による白錆発生が認められ、断面ＳＥＭ写真から、基材とその上層の放射線遮蔽コーティング間で、浮き及び剥離が無いことが認められる。実施例４〜６で赤錆無し、Ａｌ皮膜の犠牲防食作用による白錆発生、実施例７で変化なしであることが認められた。 In Examples 1 to 3, there was no red rust, white rust was generated due to the sacrificial anticorrosive action of the Al film, and from the cross-sectional SEM photograph, it was recognized that there was no floating and peeling between the base material and the radiation shielding coating on the upper layer. It was confirmed that there was no red rust in Examples 4 to 6, generation of white rust due to the sacrificial anticorrosive action of the Al coating, and no change in Example 7.
比較例１〜５で早期に赤錆、変色が認められた。封孔処理にエポキシ樹脂を用いた比較例２では変化無しであった。比較例１、３、４で基材とその上層の放射線遮蔽コーティング間で、浮き及び剥離の発生が認められる。比較例６〜８で赤錆、変色が生じ、基材とその上層の放射線遮蔽コーティング間で、浮き及び剥離の発生が認められた。 In Comparative Examples 1 to 5, red rust and discoloration were recognized early. In Comparative Example 2 where an epoxy resin was used for the sealing treatment, there was no change. In Comparative Examples 1, 3, and 4, the occurrence of floating and peeling is observed between the base material and the radiation shielding coating on the upper layer. In Comparative Examples 6 to 8, red rust and discoloration occurred, and floating and peeling were observed between the base material and the upper radiation shielding coating.
各実施形態及び各実施例は例示であり本発明を限定しない。上記の実施形態及び実施例では、基材上で、放射線遮蔽コーティング及び犠牲防食層の２層構造、防水層、放射線遮蔽コーティング及び犠牲防食層の３層構造とした放射線遮蔽コーティング部材を説明した。基材上の層構造はこれらに限定されず、放射線遮蔽コーティング及び犠牲防食層を有していれば、基材上で４層、又は５層以上の構造となっていてもよい。放射線遮蔽コーティング、犠牲防食層、防水層とは異なる機能を有する他の機能層を追加してもよい。例えば、基材から順に、放射線遮蔽コーティング、異なる素材の２層の犠牲防食層の３層構造とすること、基材から順に、防水層、他の機能層、放射線遮蔽コーティング、犠牲防食層の４層構造とすること等が挙げられる。本発明の放射線遮蔽コーティング部材は、放射性廃棄物の収集、運搬などに用いられる容器だけでなく、あらゆる用途へ用いることができる。例えば、原子力関連施設の放射線遮蔽付き設備、各種の放射線装置（工業用検査、フィルム表面改質、医療診断・治療、殺菌処理、異物検査装置）、各種の放射線照射作業（γ線、Ｘ線、電子線）における放射線遮蔽部材等への幅広い適用が可能である。 Each embodiment and each example are illustrative and do not limit the present invention. In the above-described embodiments and examples, the radiation shielding coating member having the two-layer structure of the radiation shielding coating and the sacrificial anticorrosion layer, the three-layer structure of the waterproof layer, the radiation shielding coating, and the sacrificial anticorrosion layer on the substrate has been described. The layer structure on the substrate is not limited thereto, and may have a structure of four layers or five layers or more on the substrate as long as it has a radiation shielding coating and a sacrificial anticorrosion layer. You may add the other functional layer which has a function different from a radiation shielding coating, a sacrificial anti-corrosion layer, and a waterproof layer. For example, a three-layer structure of a radiation shielding coating and two layers of sacrificial anticorrosion layers of different materials in order from the base material, and a waterproof layer, other functional layers, a radiation shielding coating, and a sacrificial anticorrosion layer in order from the base material. For example, a layer structure may be used. The radiation shielding coating member of the present invention can be used not only for containers used for collecting and transporting radioactive waste, but also for every application. For example, facilities with radiation shielding in nuclear facilities, various types of radiation equipment (industrial inspection, film surface modification, medical diagnosis / treatment, sterilization treatment, foreign matter inspection equipment), various types of radiation irradiation work (γ rays, X-rays, Wide application to radiation shielding members in electron beams).
１、１０ 放射線遮蔽コーティング部材
２、１１ 基材
３、１３ 放射線遮蔽コーティング
４、１４ 犠牲防食層
１２ 防水層
DESCRIPTION OF SYMBOLS 1,10 Radiation shielding coating member 2,11 Base material 3,13 Radiation shielding coating 4,14 Sacrificial anticorrosion layer 12 Waterproofing layer
Claims (12)
前記基材の表面に形成された放射線遮蔽コーティングであって、Ｗ、Ｍｏのうち１種以上の元素を主成分とする材料よりなる放射線遮蔽コーティングと、
前記放射線遮蔽コーティングの表面に形成された金属製の犠牲防食層であって、前記基材に対して低い標準電極電位を有する犠牲防食層と、
を備えることを特徴とする放射線遮蔽コーティング部材。 A substrate;
A radiation shielding coating formed on the surface of the substrate, wherein the radiation shielding coating is made of a material mainly composed of one or more elements of W and Mo.
A sacrificial anticorrosion layer made of metal formed on the surface of the radiation shielding coating, the sacrificial anticorrosion layer having a low standard electrode potential with respect to the substrate;
A radiation shielding coating member comprising:
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