国产ZIRLO合金动态水腐蚀氧化膜微观研究

针对反应堆用国产ZIRLO合金,采用内加热方式在346.7 ℃、15.5 MPa、含650 mg/L硼和3.5 mg/L锂溶液的条件下开展腐蚀模拟实验。利用光学显微镜、透射电子显微镜、惰性气体脉冲熔融红外吸收等方法,对腐蚀时间为2、18、250 d的氧化膜进行表征。结果表明：国产ZIRLO合金腐蚀氧化膜的主要晶体结构是柱状晶和等轴晶,随着腐蚀时间的增加,氧化膜外层柱状晶逐渐向等轴晶转变,导致晶界密度增大,氧的扩散通道增多;第二相颗粒以含Nb和含Fe、Nb为主,呈椭球形;氧化膜中的第二相颗粒未发生氧化;氧化膜中的孔隙和微裂纹随着腐蚀时间的增加而增加,主要位于氧化膜中拉应力集中区域;随着腐蚀时间的增加,锆基体中氢含量从10 ppm增至80 ppm,氢化物尺寸从几十μm增大至几百μm,呈周向分布。     

H、He离子辐照对国产ZIRLO合金氧化膜的影响

针对国产ZIRLO合金开展了H、He离子辐照对其腐蚀性能影响的研究。对国产ZIRLO合金样品分别进行高温（300 ℃）H、He离子辐照试验,辐照峰值剂量为1 dpa,之后进行模拟一回路腐蚀试验。通过腐蚀增重方法得到腐蚀动力学曲线。利用慢正电子湮没多普勒展宽谱对未辐照样品和辐照样品进行微观结构表征,用透射电子显微镜对腐蚀125 d的样品进行微观结构表征。结果表明,H、He离子辐照并未改变ZIRLO合金的腐蚀机理。He离子辐照产生的空位团可促进腐蚀过程中裂纹形核,增加了氧扩散通道,减少氧扩散激活能,导致腐蚀初期有明显的加速效应。H离子辐照对腐蚀的加速现象不如He离子辐照明显,原因是H离子辐照产生H-空位复合缺陷对氧扩散激活能减少作用较小。     

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。     

显微组织对ZIRLO锆合金耐腐蚀性的影响

将ZIRLO锆合金样品分别进行1000℃-0.5h／560℃-10h、1000℃-0.5h／冷轧／560℃-10h和750℃-0.5h、750℃-0.5h/560℃-10h、750℃-0.5h／冷轧／560℃-10h的不同处理。用透射电镜观察了它们的显微组织，将它们放入高压釜中，研究了在350℃，16.8MP,0.04M LiOH水溶液中的耐腐蚀性能，结果表明，在本文所有的变形及热处理条件下中，750℃-0.5/冷轧／560℃-10h处理后样品的耐腐蚀性能最好，其原因在于样品经过这样处理后，基体αZr中固溶的Nb含量较低，并获得了纳米尺寸分布的βNb(含Fe)第二相粒子，后者对改善耐腐蚀性能尤为重要。样品在最终560℃加热处理之前的冷轧变形，可以促进βZr分解时的形核，是获得纳米尺寸βNb的必要措施。     

热挤压690合金管材在高温水中的长期均匀腐蚀行为

采用长期浸泡和表面膜俄歇电子能谱（AES）与扫描电子显微镜（SEM）分析方法研究了热挤压690合金管材3段不同挤出顺序的管段（头部A、中部B和尾部C）在高温除氧水中的均匀腐蚀行为与机理。结果表明：热挤压690合金管材头部A、中部B和尾部C 3种试样在浸泡2 500 h后均匀腐蚀均达到稳定状态,其均匀腐蚀速率均低于5 mg/(月•dm²);头部A与尾部C的腐蚀速率相当,而明显低于中部B的腐蚀速率;氧化膜呈双层结构特征,即外层富Fe和Ni、内层富Ni和Cr,A与C试样氧化膜中间层存在铬壁垒,而B试样无明显的铬壁垒。     

Protective Oxide Film on Alloy X750 Formed in Air at 973 K

An effective pre-oxidation method for Alloy X750 was developed to reduce general corrosion in an oxygenated aqueous environment such as in BWR core water. The optimum condition of preoxidation in air at elevated temperatures was found to be 5–20 h at 973 K by considering the allowance condition of heat treatment for age-hardening.

Some characteristics of the corroded oxide film have been clarified by surface analyses with XMA, SIMS, AES, XPS etc. The film was composed of double oxide layers, namely a highly crystallized NiFe₂O₄ outer layer and a high Cr₂O₃ content inner layer. The passive property of the film has been recognized to be due to the nature of the oxides whereby NiFe₂O₄ restricts the dissolution of metals because of its low solubility and Cr₂O₃ restricts the diffusion of metal ions because of its high binding energy and low diffusion coefficient.     

锌对镍基690合金均匀腐蚀影响的XPS分析

在不加锌和加锌浓度为50ppb的两种模拟压水堆一回路水质环境下,对镍基690合金的腐蚀行为进行了研究。经过腐蚀浸泡1 500h后,用X射线光电子能谱(XPS)对其表面氧化膜结构进行深度分析。结果表明,Zn对内层氧化膜内的NiCr₂O₄和FeCr₂O₄中的Ni和Fe起到了置换作用,形成了ZnCr₂O₄。     

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。     

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。     

Influence of Dissolved Hydrogen on Structure of Oxide Film on Alloy 600 Formed in Primary Water of Pressurized Water Reactors

In order to investigate the relationship between the susceptibility of primary water stress corrosion cracking (PWSCC) in Alloy 600 and the content of dissolved hydrogen (DH) in the primary water of pressurized water reactors (PWR), structural analysis of oxide films formed under four different DH conditions in simulated primary water of PWR was carried out using a grazing incidence X-ray diffractometer (GIXRD), a scanning electron microscope (SEM) and a transmission electron microscope (TEM). In particular, to perform accurate analysis of the thin oxide films, the synchrotron radiation of SPring-8 was used for GIXRD.

It has been observed that the oxide film is mainly composed of nickel oxide, under the condition without hydrogen. On the other hand, needle-like oxides are formed at 1.0 ppm of DH. In the environment of 2.75 ppm of DH, the oxide film has thin spinel structures. From these results and phase diagram consideration, the condition around 1.0 ppm of DH corresponds to the boundary between stable NiO and spinel oxides, and also to the peak range of PWSCC susceptibility. This suggests that the boundary between NiO and spinel oxides may affect the SCC susceptibility.     

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.     

Microstructure and Corrosion Behavior about Zr-Cu-Cr Alloy

Seven kinds of Zr-Cu-Cr alloy samples were prepared by using crystalline zirconium as the base material, through normalized processing and annealing at 600 ℃/5 h. The corrosion tests were carried out in static autoclave with different water chemistry conditions, and the microstructures of alloys were studied by using EBSD, SEM and TEM to investigate the effects of Cu and Cr interaction on the microstructure and corrosion resistance of zirconium alloys. The results show that the addition of Cu element refines the recrystallized grains. When the Cr content is 1.0%, it has grains with a size of 40 μm or more. There are two kinds of second phases in Zr-Cu-Cr alloys. Zr₂Cu phase (bct) with a size of 100 nm or more and ZrCr₂ phase (hcp) with a size of 60 nm or less. As the content of Cu increases, the number of Zr₂Cu increases. As the content of Cr increases, the size of ZrCr₂ phase does not change obviously, but the number and distribution band density increase. When exposed to the superheated steam at 400 ℃/10.3 MPa, the corrosion resistance of Zr-0.3Cu-0.2Cr and Zr-0.3Cu-0.5Cr alloys is worse, the other alloys still don’t have corrosion transition after corroding 100 days, and the corrosion resistance is better. Zr-1.0Cr alloy has the best corrosion resistance. When exposed to the 360 ℃/18.6 MPa/0.01 mol/L LiOH aqueous solution for 42 days, all of alloys have poor corrosion resistance, and the addition of Cu element reduces their corrosion resistance.     

热处理工艺对冷旋U-6.5Nb合金电化学腐蚀行为的影响

采用冷旋方法制备了管状U-6.5Nb合金零件,分别在400、600和700℃下对合金零件进行1h退火处理,考察了不同状态的U-6.5Nb合金在含50μg/gCl-的氯化钾水溶液中的电化学腐蚀行为,采用扫描电镜表征了腐蚀前后的形貌特征。结果表明：所有状态的合金均未发生钝化,冷旋态和700℃退火态合金为单相组织,具有较高的腐蚀电位和较小的腐蚀电流,400℃退火和600℃退火态合金为双相组织,具有较低的腐蚀电位和较大的腐蚀电流。单相合金比双相合金具有更好的抗腐蚀能力,但更易发生点蚀。双相合金表面Nb成分不均是其抗腐蚀性不佳的主要原因。     

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。     

新锆合金碘致应力腐蚀性能研究

研究了再结晶状态的相同成分，不同织构取向的两块新锆合金板材在不同的实验条件下的抗碘致应力腐蚀性能。用直流电位降法动态监测裂纹的长度并对试样进行了织构的测定、第二相的观察和断口分析结果表明，在实验条件下，N18-2(L-T)抗碘致应力腐蚀的能力优于N18-1(T—L)断口形貌表明，在应力腐蚀裂纹的初始扩展阶段，断口沿晶开裂；在裂纹的稳态扩展阶段，以穿晶准解理扩展为主。     

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.     

镍基合金825在超临界水中的腐蚀性能研究

研究了镍基合金825在550 ℃/25 MPa、600 ℃/25 MPa和650 ℃/25 MPa超临界水（SCW）中的应力腐蚀开裂敏感性,以及在超临界650 ℃/25 MPa、次临界290 ℃/15.2 MPa水中的均匀腐蚀性能。通过慢应变速率拉伸实验得到了相应的应力-应变曲线,结果表明,随温度的升高,825的机械强度和塑性逐渐下降;实验后试样的SEM图像表明,825在3种工况下的应力腐蚀开裂倾向大小关系为600 ℃＞550 ℃＞650 ℃。825在SCW条件下的腐蚀实验表明,其腐蚀增重大致符合幂函数生长规律;而其在次临界条件下的腐蚀增重变化却呈现出先减后增的特征。     

钛膜表面氧化层对吸氘性能的影响

利用金属氢化物热力学和动力学参数测试系统对表面具有氧化层的钛膜进行了恒温吸氘和变温吸氘实验。结果表明：试样恒温吸氘时。吸氘速率随氧化层厚度的增加而变慢，达到吸氘平衡的时间也变长；试样变温吸氘时，在相同的升温速率和相同的初始氘气压力下，吸氘温度随氧化层厚度的增加而升高，表明钛膜表面氧化层具有一定的阻氘性能。