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Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金在400 ℃含氧過熱蒸汽中的腐蝕行為
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作者單位:

1.上海大學(xué)材料研究所;2.上海大學(xué)微結(jié)構(gòu)重點實驗室

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國家自然科學(xué)基金資助(項目號51871141)


Corrosion behavior of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy in 400℃ super-heated steam with oxygen
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1.Institute of Materials,Shanghai University;2.Laboratory for Microstructures,Shanghai University

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    摘要:

    為了探究Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge(質(zhì)量分?jǐn)?shù),%)合金在400 ℃/10.3 MPa不同氧含量過熱蒸汽中的腐蝕行為,將Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金樣品分別放入靜態(tài)高壓釜和動態(tài)高壓釜中進(jìn)行400 ℃/10.3MPa的除氧、300 ppb 溶解氧(DO)和1000 ppb DO過熱蒸汽腐蝕試驗。采用掃描電子顯微鏡、透射電子顯微鏡、X射線光電子能譜等表征手段對合金和氧化膜的顯微組織以及氧化膜中各元素的價態(tài)進(jìn)行分析。結(jié)果表明,與除氧環(huán)境相比,Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金在300 ppb DO和1000 ppb DO環(huán)境中的平均腐蝕速率分別增加了23.5%和29.4%,這說明DO會加速合金的腐蝕,且DO含量越高腐蝕加速作用越明顯;DO不但促進(jìn)了氧化膜中Fe、Cr、Sn和Ge等合金元素的氧化,還會加速O/M界面處Zr→ZrOx→ZrO2的演化過程; 基于以上兩個方面提出了一種DO加速鋯合金在400 ℃/10.3 MPa過熱蒸汽中腐蝕的機(jī)制:腐蝕環(huán)境中DO含量的增加導(dǎo)致氧化膜中參與反應(yīng)的O2-和OH-的濃度增加,這一方面加速了氧化膜中合金元素的氧化,導(dǎo)致氧化膜中缺陷濃度增加和局部附加應(yīng)力增大;另一方面加速了O/M界面處Zr→ZrOx→ZrO2的演化,使O/M界面處產(chǎn)生更大的應(yīng)力,提供更短的應(yīng)力馳豫時間。這兩方面的作用都會促進(jìn)氧化膜中孔隙、裂紋等缺陷的生成,加速O2-和OH-的擴(kuò)散,進(jìn)而加速了合金的腐蝕。

    Abstract:

    In order to explore the corrosion behavior of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge (mass fraction, %) alloy in 400 ℃ super-heated steam with different oxygen contents, Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy specimens were put into static autoclave and dynamic autoclave for super-heated steam corrosion tests under deaeration, 300 ppb dissolved oxygen (DO) and 1000 ppb DO environment at 400 °C/10.3 MPa, respectively. The scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscope were used to characterize the microstructure of alloys and oxide films, as well as the valence state of the alloying element. Results show that compared with the deaeration environment, the average corrosion rate of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy in 300 ppb DO and 1000 ppb DO environments increases by 23.5% and 29.4%, respectively, indicating that DO can accelerate the corrosion of the alloys, and the higher the DO content, the more obvious the corrosion acceleration effect. DO not only promotes the oxidation of Fe, Cr, Sn and Ge in the oxide film, but also accelerates the reaction process of Zr→ZrOx→ZrO2 in the transition layer at the O/M interface. Based on the above two aspects, a mechanism of DO accelerating the corrosion of zirconium alloys at 400 °C/10.3 MPa is proposed: The increase in DO content in the corrosive environment leads to an increase in the concentration of O2- and OH- participating in the reaction in the oxide film. On one hand, this promotes the oxidation of alloying elements, leading to the increase of defects in number and local stress in the oxide film; on the other hand, this also accelerates the evolution of Zr→ZrOx→ZrO2 at the O/M interface, resulting in higher stress in the oxide film and providing less time for stress release during oxidation. The roles of the two aspects both promote the generation of pores and cracks, and accelerate the diffusion of O2- and OH-, thus accelerate the corrosion of zirconium alloys.

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徐詩彤,姚美意,白勇,黃建松,林曉冬,胡麗娟,謝耀平,梁雪,彭劍超,徐靜,周邦新. Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金在400 ℃含氧過熱蒸汽中的腐蝕行為[J].稀有金屬材料與工程,2023,52(5):1746~1758.[Xu Shitong, Yao Meiyi, Bai Yong, Huang Jiansong, Lin Xiaodong, Hu Lijuan, Xie Yaoping, Liang Xue, Peng Jianchao, Xu Jing, Zhou Bangxin. Corrosion behavior of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy in 400℃ super-heated steam with oxygen[J]. Rare Metal Materials and Engineering,2023,52(5):1746~1758.]
DOI:10.12442/j. issn.1002-185X.20220229

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  • 收稿日期:2022-03-22
  • 最后修改日期:2022-06-10
  • 錄用日期:2022-06-13
  • 在線發(fā)布日期: 2023-06-08
  • 出版日期: 2023-05-29