ZIRLO合金和Zr-4合金在LiOH水溶液中耐腐蚀性能的研究

比较了ZIRLO合金和Zr-4合金两种样品在350℃、16．8MPa、0．04MLiOH水溶液中的耐腐蚀性能，发现Zr4合金样品在腐蚀转折之前的腐蚀增重比ZIRLO合金稍低，这时两种样品的氧化膜相对完整而致密。用二次离子质谱仪(SIMS)测量Li^ 在两种合金样品氧化膜剖面中的分布，发现Li^ 进入Zr-4合金氧化膜的深度比ZIRLO合金浅，但浓度比较高。而腐蚀至68天在Zr—4合金样品腐蚀发生转折后，其腐蚀增重远高于ZIRLO合金，这是因为此时Zr-4合金样品氧化膜因疏松而失去保护作用，而ZIRLO合金样品腐蚀至82天氧化膜仍致密而完整。ZIRLO合金中细小的βNb和Zr—Fe—Nb第二相粒子可能对保持氧化膜的完整性有重要作用。     

Zr-Fe-Nb合金中Zr(Nb,Fe)2相在400 ℃/10.3 MPa过热蒸汽中的腐蚀行为

Zr-1.0Fe-1.0Nb合金经β相油淬、冷轧变形及580 ℃/5 h退火处理,在静态高压釜中进行400 ℃/10.3 MPa过热蒸汽腐蚀试验,利用带EDS的SEM和HRTEM对合金基体以及腐蚀生成的氧化膜显微组织进行分析。结果表明：合金中主要存在正交的Zr 3Fe和密排六方的Zr(Nb,Fe)₂第二相。Zr(Nb,Fe)₂相在氧化过程中先转变成非晶组织,非晶进一步氧化转化为m-Nb₂O₅和m-Fe₂O₃相纳米晶态氧化物,最后扩散流失到腐蚀介质中;Zr(Nb,Fe)₂相氧化后的Fe、Nb元素发生扩散流失,且Nb的流失速度大于Fe,合金元素的扩散流失在氧化膜中留下大量缺陷,促进氧化膜由柱状晶向等轴晶形态演化而不利于合金的耐腐蚀。     

两种锆合金显微组织与腐蚀机理研究

根据国产C锆合金与低锡Zr-4合金在纯水以及LiOH水溶液中的高压釜腐蚀试验的结果,采用透射电镜（TEM）观察基体和氧化膜显微组织,通过分析氧化增重数据,对C锆合金的腐蚀机理进行了研究。提出了3种腐蚀机理:即Nb元素有效抑制阴离子空位浓度提高,可减少氧元素扩散速率;缺陷阱的数量影响氧扩散带来的腐蚀,且空位阱数量与第二相颗粒总表面积成正比;第二相粒子氧化膨胀造成氧化膜压应力松弛,降低其稳定性并失去保护能力。      

Zr-0.2Cu-xNb合金的显微组织及腐蚀行为

对Zr-0.2Cu-xNb（质量分数x=0.2,0.5,1.0,2.5）合金进行真空β相油淬、冷轧及退火处理,并在静态高压釜中进行过热蒸汽腐蚀试验,最后采用扫描电镜和透射电镜研究了合金及其腐蚀生成的氧化膜的显微组织。结果表明,随着Nb含量的增加,Zr-0.2Cu-xNb合金中Zr2Cu第二相的数量逐渐减少,而β-Zr第二相数量逐渐增加;合金中尺寸较小的Zr2Cu第二相对耐腐蚀性能有利;β-Zr第二相在氧化过程中会促进氧化膜微裂纹的产生,降低合金的耐腐蚀性能。Zr-0.2Cu-xNb合金中Nb含量接近其在α-Zr中最大固溶度时,合金具有最优的耐腐蚀性能。      

Zr-0.8Sn-1Nb-0.3Fe合金Kr~+离子辐照后的耐腐蚀性能研究

采用高压釜腐蚀实验研究了2种不同制备工艺下的Zr-0.8Sn-1Nb-0.3Fe合金(1#,2#)经360℃、5~25dpa的Kr~+辐照后、在400℃/10.3 MPa过热蒸汽中的耐腐蚀性能,用透射电子显微镜(TEM)、扫描电镜(SEM)、X射线衍射仪(XRD)分析合金腐蚀后氧化膜显微组织结构。结果表明,100 d腐蚀后,合金的腐蚀增重随着辐照剂量的增加而增加,由于1#合金中的第二相比2#合金更为细小、弥散,相同辐照剂量下,前者的腐蚀增重较低。腐蚀转折前,从蒸汽腐蚀侧到锆合金基体,氧化膜中的氧含量逐渐降低,靠近蒸汽侧的氧化膜主要由等轴晶形态的单斜ZrO_2组成,而基体界面处的氧化膜主要为柱状晶形态的四方ZrO_2和六方Zr_3O;腐蚀转折后,基体界面处的氧化膜呈"花菜"状生长,"花菜"尺寸大小与氧化膜生长速率的高低及不均匀生长趋势的大小呈对应关系。     

国产压水堆核电站40 GW•d/tU乏燃料棒金相检验

为评价国产燃料棒在较高燃耗水平下的辐照性能,在中国原子能科学研究院燃料与材料检验设施（303热室）对燃耗为40 GW•d/tU的国产压水堆核电站乏燃料棒进行了金相检验。检验内容包括芯块宏观与微观组织、包壳水侧腐蚀与氢化物分布、芯块-包壳相互作用状况等。金相检验结果表明：40 GW•d/tU燃耗下,芯块未发生明显的轮廓变化,气孔率为3.3%～5.8%,晶粒组织为等轴晶,平均晶粒尺寸为7.2 μm;Zr合金最大水侧氧化膜厚度为23 μm,氢化物分布和含量正常,最大氢含量约为150 μg/g,同时不同部位的包壳氢含量与水侧氧化膜厚度基本呈线性关系,水侧腐蚀处于正常水平;包壳内壁有局部轻微腐蚀,包壳与芯块之间存在间隙,未发生包壳与芯块相互作用情况。     

Zr-Sn-Nb-Fe合金显微组织及耐腐蚀性能研究

将Zr-Sn-Nb-Fe合金样品冷轧后在500和560℃下分别保温不同时间,在350℃、16.8MPa、含70μg/gLi⁺的LiOH水溶液中腐蚀,500℃/100h样品的耐腐蚀性能最好。用透射电镜（TEM）研究了这些样品的显微组织和第二相,观测到随着保温时间延长,500℃下保温样品中的第二相由连续片层逐渐转变成带状分布的颗粒,保温时间达到100h时,基体内析出βNb。560℃下保温样品与500℃下保温样品有相似的组织转变过程,只是时间大幅缩短,保温仅10h时,基体已完全再结晶为等轴晶。     

Zr-Nb合金在LiOH水溶液中耐腐蚀性的研究

比较了Zr-Nb合金与Zr-Sn-Nb-Fe及Zr-4合金的耐腐蚀性，讨论了Nb对Zr-Nb合金在不同介质中耐腐蚀性的影响，实验证明Nb的腐蚀产物可以部分溶解于LiOH水溶液中，因而Zr-Nb合金在LiOH水溶液中腐蚀时，合金中β－Nb第二相腐蚀后生成的腐蚀产物会部分溶解于LiOH水溶液，在氧化膜中形成孔洞，从而导致Zr-Nb合金在LiOH水溶液中的耐腐蚀性变差。     

锆合金在高温高压水中的腐蚀

本文介绍了国产锆-2、锆-4合金在温度大于300℃的水或蒸汽中的腐蚀——氧化与吸氢;认为两种合金耐氧化性能相似,在反应堆工质中使用,具有足够的耐蚀性。水中添加少量氢氧化锂(含锂1—2ppm)或硼酸(含硼800ppm),对合金腐蚀无明显影响。在高温水中,锆-4在腐蚀300天后的吸氢增重约为锆-2的1/3—1/2;而在341℃蒸汽中,锆-4减少吸氢的优越性并不明显。水中加氢增加了锆-4的吸氢速率,但并没有达到妨碍使用的程度。预生氧化膜不能改善合金的耐长期腐蚀性能。具有热流的锆合金管与不锈钢定位架接触处的隙缝会导致危险的局部腐蚀,但在中性水条件下,腐蚀深度很浅,并不影响锆合金的长期使用。     

候选材料在650 ℃超临界水中的腐蚀行为研究

研究了3种候选材料（347、HR3C和In-718）在650 ℃、25 MPa去离子水中的均匀腐蚀行为,使用场发射扫描电镜（FEG-SEM）和能谱（EDS）观察了不同腐蚀时间的表面氧化膜形貌与合金元素分布,使用掠入射X射线衍射（GIXRD）分析了氧化膜相结构。结果表明,3种材料腐蚀失重均符合抛物线规律,347的失重为HR3C和In 718的40倍以上;3种材料氧化膜均以Ni(Cr, Fe) ₂O₄为主,In-718点蚀严重,347氧化膜明显脱落,HR3C氧化膜较均匀致密;高温超临界水中,提高合金的Cr含量有助于增强均匀腐蚀性能,添加Nb有损合金的点蚀抗力。     

Study of Oxide Film Formed on Domestic ZIRLO Alloy in Stimulate Corrosion Environment

By using the internal heating method, reactor stimulation loop corrosion experiments were carried out in the solution containing 650 mg/L boron and 3.5 mg/L lithium, at the temperature of 346.7 ℃ and pressure of 15.5 MPa, to study the properties of domestic ZIRLO. The optical microscope, transmission electron microscope and pulse heating inert gas fusion infrared absorption method were selected to characterize the ZILRO samples corroded for 2, 18, 250 d. The results show that the main types of the grains of oxide film formed on domestic ZILRO are columnar grains and equiaxed grains. As the corrosion time increasing, the columnar grains located at the outer part of the oxide film gradually transform into equiaxed grains, which will lead to the increase of the grain boundary density and oxygen diffusion channels. The main types of second phase particles are containing Nb particles and containing Fe and Nb particles respectively, with the shape of ellipsoid. The corrosion process does not change the structure and content of the second phase particles, and most of the particles embed in oxide films remained un-oxidized state. With the increase of corrosion time, the number and the size of the pores and microcracks in the oxide film also increase, and most of these cracks are located at the wave peak of the O/M interface or the second phase particles due to the tensile stress effects. As for the hydrides generated from the corrosion reaction, the content of these hydrides increases from 10 ppm to 80 ppm, and the size increases from tens of microns to hundreds of microns, which are mainly distributed circumferentially.     

Effect of β phase, precipitate and Nb-concentration in matrix on corrosion and oxide characteristics of Zr-xNb alloys

The corrosion test and oxide characterization were performed on the specimens having different Nb-content in the range of 0-5 wt%. The specimens were heat-treated at 570 °C for 500 h to get the α+β_Nb phase and at 640 °C for 10 h to get the α+β_Zr phase after β-quenching. The corrosion tests were carried out at 360 °C. In the low Nb-contents of 0.1-0.2 wt% where Nb was soluble in the matrix without the formation of Nb-containing precipitates or β phase, the samples showed the excellent corrosion resistance and their corrosion resistance was not affected by heat-treatment. The corrosion resistance was improved by the stabilization of tetragonal ZrO₂ and columnar oxide structure when all added Nb was soluble in the matrix to equilibrium concentration. In the high Nb-contents of 1.0-5.0 wt%, the corrosion rate was very sensitive to the annealing condition. The transformation of oxide crystal structure from tetragonal ZrO₂ to monoclinic ZrO₂ and oxide microstructure from columnar to equiaxed structure was accelerated in the samples having β_Zr phase, while retarded in the sample having β_Nb phase. This means that the formation of β_Nb phase resulted in the reduction of Nb concentration in the α matrix, thus the corrosion resistance was enhanced with the formation of β_Nb phase. From the corrosion test and oxide characterization, it is suggested that the equilibrium concentration of Nb in the α matrix would be a more dominant factor to enhance the corrosion resistance than the Nb-containing precipitates, supersaturated Nb, and β phase (β_Nb or β_Zr).     

The Effect of Oxide Microstructure on Kinetic Transition in Out-of-pile Steam Corrosion Test for Zircaloy-2 and Nb-added Zircaloy-2

In order to study the mechanism of kinetic transition of corrosion rate for zirconium alloys, oxide films formed on Zircaloy-2 (Zry-2) and Nb-added Zircaloy-2 (0.5Nb/Zry-2) in steam at 673 K and 10.3 MPa were examined with TEM and SIMS.

Kinetic transition occurred at almost the same oxide thicknesses for both Zry-2 and 0.5Nb/Zry-2, but the corrosion rate after the transitions were quite different for the two alloys. Zircaloy-2 showed cyclical oxidation, while the weight gain of 0.5Nb/Zry-2 increased linearly.

The morphology and crystal structure were similar for the oxides of the two alloys and both the oxide films still mainly consisted of columnar grains even after the transition. Interface layers which mainly consisted of a-Zr crystallites were observed for both alloys and the oxygen content in the interface layers increased after the transition.

The solute concentrations of Fe, Cr and Ni became higher, accompanying the increase of oxygen concentrations at columnar grain boundaries in the oxide films after the transition for 0.5Nb/Zry-2. It was thought that the properties of grain boundaries of the 0.5Nb/Zry-2 oxide films changed after the transition, and the increase in oxygen diffusivity at grain boundaries caused the linear increase in weight gain.     

α+β两相区热处理对Zr-Sn-Nb合金微观组织和腐蚀性能的影响

对Zr-Sn-Nb合金在α+β两相区温度下不同工艺热处理后所得样品,在360 ℃/18.6 MPa纯水环境中进行均匀腐蚀试验,并采用扫描电子显微镜（SEM）观察样品微观形貌、聚焦离子束（FIB）和原子力显微镜（AFM）分析腐蚀后样品表面氧化膜。结果表明,Zr-Sn-Nb合金在α+β两相区温度下热处理时,锆合金中会形成条带状β-Zr第二相,再经过α相区温度最终退火后,β-Zr区域会分解为α-Zr和第二相粒子;经α相区最终退火的样品,在360 ℃/18.6 MPa纯水中的耐腐蚀性能优于未经最终退火的样品;未退火样品中条带状β-Zr第二相区域的氧化膜较α-Zr基体的氧化膜厚,而经过α相区温度退火后β-Zr发生分解,该区域的腐蚀氧化膜出现凹陷。     

Influence of second phase particles on corrosion resistance of N36 alloy in superheated steam

The nodular corrosion resistance of N36 (Zr–0.8Sn–1Nb–0.3Fe–0.12O, wt%) alloy with different temperatures of interstage annealing and optimized Zircaloy-4 (lower content of tin) cladding tubes were tested in 500 °C and 10.3 MPa superheated steam. The result showed that no nodular spots appeared on surface of N36 alloy cladding tubes after 500 h corrosion, while nodular spots on optimized Zircaloy-4 tubes after 8 h. The differences of weight gain between two kinds of N36 tubes suggested that the percentage (volume fraction) of tetragonal Zr dioxide in oxide film can be effectively influenced by characteristics, such as size, of the second phase particles on the oxide film-matrix boundary. The analysis by SEM and LRS clearly indicated that smaller and fine distributed second phase particles were beneficial to stabilize the oxide via endure the uniform stress so it could slow down the altering process from tetragonal Zr dioxide to monoclinic Zr dioxide.     

Effect of Heat Treatment in α+β Phase Field on Microstructure and Corrosion Property of Zr-Sn-Nb Alloy

Uniform corrosion tests were carried out with the specimens prepared by different heat treatments at the temperature in α+β phase field. The surface microstructure of specimens was observed by scanning electron microscope, the corrosion behavior was analyzed by autoclaves, and the oxide layer on the surface after the corrosion test was analyzed by focused ion beam (FIB) and atomic force microscope (AFM). The results show that after the heat treatment in α+β phase field, lamellar β-Zr phase appeares in the Zr matrix, and after the subsequent α phase final heat treatment, the β-Zr phase will be decomposed to α-Zr and discontinuous second phase particles. For the specimens heat treated in α+β phase field, after the α phase final heat treatment, the corrosion resistance under 360 ℃/18.6 MPa pure water condition is better than that of specimens without final heat treatment. The oxide film formed on the β-Zr protrudes on the oxide surface, on the contrary, after α phase final heat treatment, β-Zr decomposes, and the oxide layer is sunken in this area.     

Corrosion characteristics and oxide microstructures of Zircaloy-4 in aqueous alkali hydroxide solutions

The corrosion characteristics of Zircaloy-4 have been investigated in various aqueous solutions of LiOH, NaOH, KOH, RbOH and CsOH with equimolar M⁺ and OH⁻ at 350°C. The characterization of the oxides was performed using transmission electron microscope (TEM) and scanning electron microscope (SEM) on the samples which were prepared to have an equal oxide thickness in pre-transition and post-transition regimes. At a low concentration (4.3 mmol) of aqueous alkali hydroxide solutions, the corrosion rates decrease gradually as the ionic radius of cation increases. At a high concentration (32.5 mmol), the corrosion rate increases significantly in LiOH solution and slightly in NaOH solution, but in the other hydroxide solutions such as KOH, RbOH and CsOH, the corrosion rate is not accelerated. Even if the specimens have an equal oxide thickness in LiOH, NaOH and KOH solutions, the oxide microstructure formed in the LiOH solution is quite different from those formed in the NaOH or the KOH solutions. In the LiOH solution, the oxides grown in the pre-transition regime as well as in the post-transition regime have an equiaxed structure including many pores and open grain boundaries. The oxides grown in the NaOH solution have a protective columnar structure in the pre-transition regime but an equiaxed structure in the post-transition regime. On the other hand, in the KOH solution, the columnar structure is maintained from its pre-transition regime to the post-transition regime. On the basis of the above results, it can be suggested that the cation incorporation into zirconium oxide would control the oxide microstructure, the oxide growth mechanism at the metal–oxide interface and the corrosion rate in alkali hydroxide solutions.