Zr-Sn-Nb-Fe-V合金包壳管加工过程中第二相的演变

采用扫描电子显微镜（SEM）和透射电子显微镜（TEM）研究了Zr-0.2Sn-1.3Nb-0.2Fe-0.05V合金经热挤压、冷轧、中间退火包壳管坯以及经终轧及最终退火后成品管材第二相特征。结果表明,热挤压产生的β-Zr及第二相沿管坯轴向呈流线状分布,随着冷轧和退火的进行,亚稳相β-Zr发生分解,第二相逐渐均匀化,最终呈细小、均匀、弥散分布。合金成品管材第二相主要为BCC结构的β-Nb,含有少量FCC结构的Zr(NbFeV)₂。加工过程中析出相的平均直径变化不大,均小于100 nm。合金包壳管第二相尺寸分布与热处理过程中含Nb第二相溶解析出直接相关。     

Zr-0.2Cu-xNb合金的显微组织及腐蚀行为

对Zr-0.2Cu-x Nb(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-x Nb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-x Nb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。     

热加工对Zr-Sn-Nb合金显微组织的影响研究

对Zr-Sn-Nb合金在4种温度(750℃、780℃、800℃和820℃)下进行了热／冷加工和最终再结晶退火,并对在上述4种温度下加热的试样进行了淬火处理。用透射电子显微镜(TEM)和光学金相显微镜(OM)研究了试样的显微组织、β-Zr以及第二相粒子的特征：结果表明,当加热温度达到780℃或高于此温度时．Zr-Sn-Nb合金已进入α-β双相区;随着加热温度的增加,β-Zr相含量增多;加工后试样中的第二相粒子大部分为C14型六方结构的Zr(Fe、Cr)2Laves相,与Zr-4合金中第二相结构相同,点阵常数α=0．502nm、c=0．818nm。同时．还发现有少量C15型面心立方结构Zr(Fe,Cr)2Laves相,点阵常数α=0．716nm．     

Zr-xSn-1Nb-0.3Fe合金在LiOH水溶液中的腐蚀行为研究

研究了不同Sn含量的Zr-xSn-1Nb-0.3Fe（x=0～1.5）合金在360 ℃、18.6 MPa、0.01 mol/L的LiOH水溶液中的耐腐蚀性能。340 d腐蚀结果表明,Sn质量含量从1.5%降低至0.6%时,合金试样的腐蚀增重明显降低,进一步降低Sn含量时,腐蚀增重反而增加;采用TEM表征合金试样的显微组织发现,随着Sn含量的变化,合金中第二相的大小及分布相似,但面密度随着Sn含量的增大而减小。分析Sn对Zr-Sn-Nb-Fe合金腐蚀行为的影响机理,认为固溶在α-Zr中的Sn含量是引起耐腐蚀性能差别的主要原因。     

注锌水化学对Zr-Sn-Nb合金腐蚀性能影响

采用高压釜腐蚀试验研究Zr-Sn-Nb合金在模拟压水堆一回路注锌水化学环境中的腐蚀行为,对Zr-Sn-Nb合金在无锌和加锌水化学环境中的腐蚀增重、氧化膜形貌等现象进行分析。结果表明:Zr-Sn-Nb合金在无锌和加锌水化学环境中腐蚀150 d时腐蚀增重曲线发生转折,加锌对Zr-Sn-Nb合金腐蚀增重量、腐蚀动力学规律、氧化膜形貌、氧化膜物相、氧化膜厚度、氢化物分布和吸氢浓度无明显影响。      

热处理对含Nb锆合金焊接试样显微组织和耐腐蚀性能的影响

用真空电子束焊接方法将Zr-1.88Sn-0.35Fe-0.52Nb合金板与Zr-4板对接焊的样品,在400C、10.3MPa过热水蒸汽中腐蚀165d后,用光学显微镜从样品横截面上测量了焊接面和其背面不同部位的氧化膜厚度,并用透射电镜观察了不同部位锆合金的显微组织。结果表明:焊接样品经过500C退火处理,耐腐蚀性能明显提高,在相同的熔区和热影响区(含Nb侧)内,经过退火和未经退火的样品表面氧化膜的厚度相差10-20倍;焊接冷却时形成的bZr在退火时分解为aZr bNb是提高耐腐蚀性能的主要原因;焊接样品经过500C-1.5h退火处理后,熔区的耐腐蚀性能非常优良,在400C过热蒸汽中腐蚀165d后,氧化膜厚度未超过2mm,折算为腐蚀增重只有30mg·dm-2。根据电子探针的分析结果,熔区中的成分大约是Zr-1.2Sn-0.25Nb-0.25Fe-0.02Cr。     

用正电子湮没技术研究新锆合金包壳的离子辐照效应

国产Zr-Sn-Nb系新锆合金SZA-4和SZA-6是CAP1400大型先进压水堆包壳材料的主要候选材料,对其辐照性能的研究可为制备工艺改进提供科学依据。在中国原子能科学研究院HI-13串列加速器辐照终端,在300 ℃温度下,用100 MeV的Fe束流对两种新锆合金包壳管材进行5 dpa剂量辐照。辐照前后的正电子湮没寿命测量表明：两种样品辐照前湮没寿命为Zr中单空位寿命,表明管材制备过程中最后的退火温度和时间尚未完全消除加工引入的缺陷;两种样品辐照后的正电子湮没寿命减小,分析表明这是由于辐照导致Fe在锆合金中重新分布,主要分布在bcc结构的β-Nb沉淀相颗粒与hcp结构的α-Zr基体之间具有开空间的相界,正电子被相界捕获,与周围Fe原子电子湮没,造成湮没寿命减小。     

Zr-Sn-Nb合金I-SCC腐蚀产物研究

利用SEM和EDXA对Zr-Sn-Nb合金碘致应力腐蚀断口上的腐蚀产物进行了观察分析。结果表明：腐蚀产物的成分主要是氧和锆，只有局部准解理断裂区域可检测到碘，碘与氧在锆基体上竞争吸附，形成不具保护作用的膜．促进局部严重氧化；应力、碘分压、合金成分及热处理状态等因素会影响腐蚀产物的特征，这些影响作用与碘的扩散、合金中第二相的数量以及Zr-I-O体系的化学平衡有关。     

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。     

锆合金氧化膜及基体中氧的扩散

锆合金氧化膜及基体中氧的扩散系数是锆合金腐蚀动力学中的重要参数,目前文献报道的氧在锆及氧化膜中的扩散系数数值差异较大。本文通过真空退火试验,得到不同温度下氧化膜中氧浓度分布,计算了氧在锆合金基体中的扩散系数;通过氧化膜的等效扩散模型,由腐蚀转折前的腐蚀增重曲线,估算锆合金氧化膜中氧的扩散系数,得到Zr-Sn-Nb合金基体中氧的扩散系数随温度的变化规律为D_Zr(cm²/s)=0.18exp(-180 000/RT);通过转折前的腐蚀增重曲线,估算得到氧化膜中氧的扩散系数随温度的变化规律为D_ox(cm²/s)=3×10^-7exp(-101 550/RT)。     

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.     

The effect of alloying modifications on hydrogen uptake of zirconium-alloy welding specimens during corrosion tests

The hydrogen uptake behavior during corrosion tests for electron beam welding specimens made out of Zircaloy-4 and zirconium alloys with different compositions was investigated. Results showed that the hydrogen uptake in the specimens after corrosion tests increased with increasing Cr content in the molten zone. This indicated that Cr element significantly affected the hydrogen uptake behavior. Fe and Cr have a low solubility in α-Zr and exist mainly in the form of Zr(Fe,Cr)₂ precipitates, which is extremely reactive with hydrogen in its metallic state. It is concluded that the presence of Zr(Fe,Cr)₂ second phase particles (SPPs) is responsible for the increase in the amount of hydrogen uptake in the molten zone of the welding samples after corrosion, as Zr(Fe,Cr)₂ SPPs embedded in α-Zr matrix and exposed at the metal/oxide interface could act as a preferred path for hydrogen uptake.     

Corrosion behavior of heat-treated Fe-Al coated steel in lead-bismuth eutectic under loading

A protective surface alloy coating on steel surfaces can prevent steels from the heavy LBE corrosion in the LBE cooled reactor. Especially, Fe-Al alloy coating on a steel surface is effective for corrosion resistance in LBE due to the self-healing of a thin and stable Al oxide layer on the surface of the coating layer. In order to investigate the utility of the coating layer under the stress due to the hydrodynamic and thermal stress induced in the practical system. The Fe-Al coated 316SS, which was heat-treated after the coating process, was immersed in the stagnant LBE at 650 °C for 250 h with loading to investigate the corrosion behavior of the specimen with the bending stress. The Fe-Al coating layer was not corroded because of the protection by Al oxide scale which was formed on the surface of the coating layer and the interface between the coating and the matrix during the heat treatment process. The coating layer cracked elastically. The LBE penetrated into the cracks and corroded the 316SS matrix and the pre-coating layer. The matrix exhibited the dissolution corrosion caused by the preferential dissolution of Ni and the oxidation forming the Fe oxide and Cr oxide. The coating layer is effective to reduce the surface of the matrix to be corroded by LBE, and can moderate the corrosion of the depth direction.     

Microstructure evolution in Zr1Nb fuel cladding during high-temperature oxidation

This work is concerned with the microstructure evolution during high-temperature oxidation inside the cladding wall fabricated of Zr1Nb alloy. The kinetics of the α-Zr(O) growth in the temperature interval of 800-1200 °C has been assessed using LM, SEM, and an image analyzer. In addition, the results of nanohardness measurement were used to determine the thickness of the α-Zr(O) layer. Eventually, the experimental results were compared to analytical calculations. Very good agreement has been achieved between experimental and theoretical results, mainly for lower thicknesses. The paper also deals with the kinetics of oxide and (α + β)-Zr layers. The oxide layer growth kinetics changes depending on temperature. The kinetics of the (α + β)-Zr layer is independent of temperature and slightly faster when compared to the parabolic growth.     

Comprehensive investigation of the corrosion state of the heat exchanger tubes of steam generators. Part I. General corrosion state and morphology

The present work, constituting the first part of a series of two, deals with a systematic investigation of the general corrosion state of 22 heat exchanger tubes originating from different steam generators of the Paks NPP (Hungary). While the passivity of the inner surface of the stainless steel tube specimens was studied by voltammetry, the morphology and chemical composition of the oxide layer formed on the surfaces were analyzed by SEM–EDX method. Based on the measured corrosion characteristics (corrosion rate, thickness and chemical composition of the protective oxide layer) a strong dependence of these parameters on the decontamination history of the steam generators was revealed. It is well documented that the chemical decontamination carried out by a non-regenerative version of the AP-CITROX procedure does exert, on the long run, a detrimental effect on the corrosion resistance of steel surfaces. Therefore, process restrictions and modifications to minimize corrosion damages have be defined.     

Results of steel corrosion tests in flowing liquid Pb/Bi at 420-600 °C after 2000 h

Corrosion tests were carried out on austenitic AISI 316L and 1.4970 steels and on MANET steel up to 2000 h of exposure to flowing (up to 2 m/s) Pb/Bi. The concentration of oxygen in the liquid alloy was controlled at 10⁻⁶ wt%. Specimens consisted of tube and rod sections in original state and after alloying of Al into the surface. After 2000 h of exposure at 420 and 550 °C the specimen surfaces were covered with an intact oxide layer which provided a good protection against corrosion attack of the liquid Pb/Bi alloy. After the same time corrosion attack at 600 °C was severe at the original AISI 316L steel specimens. The alloyed specimens containing FeAl on the surface of the alloyed layer still maintained an intact oxide layer with good corrosion protection up to 600 °C.     

TiD_(1.92)热解析的动力学行为研究

采用热分析和理论计算的方法对TiD1.92粉末的解析行为进行了研究。计算的TiD1.92粉末有3类解析峰,均与TiD1.92解析中发生相变导致的氘扩散速率变化有关。球形颗粒模型的解析与平板颗粒模型的解析因其相变和扩散机制不同导致β→α相变解析峰表现出一定的差异。TiD1.92粉末的热分析结果与平板颗粒模型的计算结果完全一致,其中δ相和β相钛氘化物的解析由表面反应控制,β→α相变阶段的解析由氘在α相的扩散控制,实验获得氘在钛表面的解析活化能为152.8kJ/mol以及氘在α相中的扩散活化能为68.6kJ/mol。