CN113293374A - 一种用于锆合金包壳管外表面的涂层及制作方法 - Google Patents

一种用于锆合金包壳管外表面的涂层及制作方法 Download PDF

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CN113293374A
CN113293374A CN202110494834.2A CN202110494834A CN113293374A CN 113293374 A CN113293374 A CN 113293374A CN 202110494834 A CN202110494834 A CN 202110494834A CN 113293374 A CN113293374 A CN 113293374A
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coating
zirconium alloy
cladding tube
alloy cladding
layer
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崔严光
李崇
卢俊强
周云清
恽迪
马大衍
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Shanghai Nuclear Engineering Research and Design Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
    • G21C3/02—Fuel elements
    • G21C3/04—Constructional details
    • G21C3/06—Casings; Jackets
    • G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Abstract

本发明公开了一种用于锆合金包壳管外表面的涂层及制作方法，所述涂层为在所述锆合金包壳管基体上依次覆上ZrN过渡层和Cr工作层；所述ZrN过渡层厚度在0.12～2μm；所述Cr工作层为主成分为氧化钇掺杂稳定氧化锆的工作层。本发明能有效抑制Cr工作层与锆合金基体之间的元素互扩散，避免在高温下Cr工作层与基体之间的元素互扩散。且在淬火条件下该ZrN层在应力作用下产生孪晶能有效缓释涂层与基体之间由于热膨胀系数不匹配产生的应力，增强涂层与基体的结合力，避免涂层的破裂失效。

Description

一种用于锆合金包壳管外表面的涂层及制作方法
技术领域
本发明涉及一种轻水反应堆用锆合金表面涂层，以显著提高锆合金包壳管耐高温蒸汽氧化性能。
背景技术
目前国内外正在开展研究，试图获得一种抗LOCA事故的核燃料元件(AccidentTorlerent Fuel，ATF)。
鉴于燃料棒具有耐磨损与抗LOCA事故中高温蒸汽腐蚀等多种需求，目前国内外正针对燃料棒的锆合金包壳开发保护性涂层，该涂层应使燃料棒兼具耐磨性和耐蒸汽腐蚀功能。Cr涂层是公认的能够同时增加燃料棒耐磨性和耐蒸汽腐蚀功能的涂层。但是在高温环境下由于Cr涂层与锆合金基体间发生元素互扩散导致涂层厚度减薄，影响其结构完整性，其次在温度高于1330℃，Cr金属与锆合金基体发生共熔反应，破坏涂层的完整性。因此，若在涂层与基体中间加屏蔽层，能够有效解决这一问题。
发明内容
本发明的目的在于为轻水反应堆燃料棒的锆合金包壳管提供一种涂层，该涂层显著提高锆合金包壳管在正常工况下的耐水腐蚀性能以及事故工况下的耐高温蒸汽腐蚀性能，能抑制涂层与基体间的元素互扩散。
一种用于锆合金包壳管外表面的涂层，所述涂层为在所述锆合金包壳管基体上依次覆上ZrN过渡层和Cr工作层；所述ZrN过渡层厚度在0.12～2μm；所述 Cr工作层为纯Cr。
优选的，所述ZrN过渡层厚度范围在0.12～1μm。
本发明还提供一种用于锆合金包壳管外表面的涂层的制作方法，其步骤如下：
第一，对所述锆合金包壳管基体进行表面预处理；
第二，对表面预处理后的所述锆合金包壳管基体进行表面氮化，得到所述ZrN过渡层；
第三，将氮化后的所述锆合金包壳管基体表面沉积Cr工作层。
采用本发明的技术方案可大幅增强现役轻水反应堆的燃料棒耐耐腐蚀能力。与性能相近的Cr涂层相比，本发明能有效抑制Cr涂层与锆合金基体之间的元素互扩散，避免在高温下Cr涂层与基体之间的元素互扩散。且在淬火条件下该ZrN 层在应力作用下产生孪晶能有效缓释涂层与基体之间由于热膨胀系数不匹配产生的应力，增强涂层与基体的结合力，避免涂层的破裂失效。
因此，本发明适用于现役轻水反应堆燃料棒，与未采用此发明的燃料棒相比，具有较强的耐高温蒸汽腐蚀性能。
附图说明
图1为本发明锆合金表面涂层截面图；
其中，1、锆合金基体，2、ZrN过渡层，3、Cr工作层；
图2为本发明的制作方法路线图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和具体实施方式对本发明作进一步详细的说明。
在锆合金包壳表面涂覆第一层为ZrN层，用于隔绝Cr工作层与Zr基体；第二层为Cr工作层，抵御高温水及高温蒸汽腐蚀。
一种用于锆合金包壳管外表面的涂层的制作方法，包括如下步骤，
第一，对所述锆合金包壳管基体进行表面预处理；
第二，对表面预处理后的所述锆合金包壳管基体进行表面氮化，得到所述 ZrN过渡层；
第三，将氮化后的所述锆合金包壳管基体表面沉积Cr工作层。
本发明实施例中的特点是：1、采用ZrN做过渡层，阻止了高温条件下工作层铬元素向锆合金基体扩散；2、阻止了高温条件下基体锆向铬涂层中的扩散；3、采用纯铬为工作层，在高温水蒸气中反应；4、ZrN过渡层仅为0.12～2μm，对涂层力学影响较小。
因此，本发明的涂层显著提高了锆合金包壳管的耐腐蚀性能，有效避免了在高温环境中涂层的失效。在锆合金表面涂覆纯铬，涂层厚度5μm。由于没有过渡层保护，高温条件下，涂层与基体发生元素互扩散，涂层厚度减薄，结构被破坏，失去了保护效果。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若对本发明的这些修改和变型属于本发明权利要求及其同等技术的范围之内，则本发明也意图包含这些改动和变型在内。上述实施例或实施方式只是对本发明的举例说明，本发明也可以以其它的特定方式或其它的特定形式实施，而不偏离本发明的要旨或本质特征。因此，描述的实施方式从任何方面来看均应视为说明性而非限定性的。本发明的范围应由附加的权利要求说明，任何与权利要求的意图和范围等效的变化也应包含在本发明的范围内。

Claims (3)

1.一种用于锆合金包壳管外表面的涂层，其特征在于，所述涂层为在所述锆合金包壳管基体上依次覆上ZrN过渡层和Cr工作层；所述Cr工作层为纯Cr。
2.如权利要求1所述锆合金包壳管外表面的涂层，其特征在于，所述ZrN过渡层厚度范围在0.12～1μm。
3.一种用于锆合金包壳管外表面的涂层的制作方法，其特征在于，其步骤如下：
第一，对所述锆合金包壳管基体进行表面预处理；
第二，对表面预处理后的所述锆合金包壳管基体进行表面氮化，得到所述ZrN过渡层；
第三，将氮化后的所述锆合金包壳管基体表面沉积Cr工作层。
CN202110494834.2A 2021-05-07 2021-05-07 一种用于锆合金包壳管外表面的涂层及制作方法 Pending CN113293374A (zh)

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CN114015959A (zh) * 2021-11-08 2022-02-08 上海核工程研究设计院有限公司 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法
CN114438493A (zh) * 2021-11-08 2022-05-06 上海核工程研究设计院有限公司 一种核电厂锆合金包壳管表面用抗高温水蒸气腐蚀涂层及其制备方法
CN115341167A (zh) * 2022-08-26 2022-11-15 西安电子科技大学 一种纳米孪晶ZrN扩散屏蔽层及其制备方法
CN115354279A (zh) * 2022-08-24 2022-11-18 西安电子科技大学 一种应用于单晶镍基合金与表面热障涂层间的扩散屏蔽层及其制备方法

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CN112164479A (zh) * 2020-08-21 2021-01-01 上海核工程研究设计院有限公司 一种锆合金包壳管耐高温蒸汽腐蚀涂层

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CN114015959A (zh) * 2021-11-08 2022-02-08 上海核工程研究设计院有限公司 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法
CN114438493A (zh) * 2021-11-08 2022-05-06 上海核工程研究设计院有限公司 一种核电厂锆合金包壳管表面用抗高温水蒸气腐蚀涂层及其制备方法
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CN115354279B (zh) * 2022-08-24 2023-11-17 西安电子科技大学 一种应用于单晶镍基合金与表面热障涂层间的扩散屏蔽层及其制备方法
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