碳钢对核主泵用奥氏体不锈钢的污染研究

奥氏体不锈钢在加工、运输和装配过程中如果与碳钢直接接触,就会被碳钢污染,而导致奥氏体不锈钢耐蚀性能的改变。众所周知,核主泵用奥氏体不锈钢对耐蚀性有着非常严格的要求,本文以Z2CN18-10核主泵用奥氏体不锈钢为例,通过FeCl3腐蚀试验和电化学方法测试了被碳钢污染后其耐腐蚀性能的变化。试验结果表明:附着在不锈钢表面的碳钢对其长期总体腐蚀速率影响不大;嵌入式的碳钢颗粒会显著降低奥氏体不锈钢的点蚀电位,增大发生点蚀的倾向;硝酸钝化可部分抵消被污染不锈钢点蚀电位的降低,但该值仍远低于同样经过硝酸钝化,而未被污染的不锈钢的点蚀电位。此外,还针对碳钢污染对核电站辐射场的影响和对燃料包壳热传导效率的影响进行了讨论。     

321不锈钢在低酸度硝酸铀酰溶液中的腐蚀特性

用称量法和电化学法研究了321不锈钢在不同浓度和pH值的硝酸铀酰溶液中的高温均匀腐蚀和电化学府蚀行为。均匀腐蚀试验结果表明．在选定的腐蚀条件下，321不锈钢样品在960h内，其表面光洁度无明显变化．腐蚀速率小于0．04mg/m^2.h，在低酸度的硝酸铀酰溶液中耐蚀。用腐蚀电入学法研究了321不锈钢在有溶解氧的硝酸铀酰溶液中的腐蚀电化学特性，测量了电极的腐蚀电位、腐蚀电流密度。经AES分析表明，电化学腐蚀后的样品在腐蚀膜中有一定量的铀．深度剖析含铀腐蚀膜的厚度为10—15nm。     

17-4PH不锈钢长期时效对电化学腐蚀行为的影响

采用恒电位阳极极化法研究了17-4PH不锈钢经长期时效后试样分别在(0.5 mol/LH2SO4+1%NaCI)溶液和1%NaCI溶液中的腐蚀行为.结果表明:17-4PH不锈钢经时效处理后点蚀电位负移,钝化膜保护性下降,材料耐蚀性能降低.17.-4PH不锈钢在含有C1-的H2SO4溶液中能发生钝化,并有较宽的钝化区域,而在1%NaCI溶液中不能形成钝化膜,Cl-对试样有严重的点蚀现象.阳极极化曲线显示,17-4PH不锈钢随着时效时间的延长耐蚀性降低,主要是由于时效处理使第二相沿晶界析出、材料组织发生改变所致.     

304奥氏体不锈钢在硝酸溶液体系中的电化学腐蚀行为

采用极化曲线测量法对304不锈钢在硝酸溶液体系中的电化学耐蚀性能进行了测试,分别研究了在硝酸溶液中添加硝酸盐、草酸、乙酸、柠檬酸等成分对304不锈钢电化学腐蚀行为的影响。结果表明,在硝酸溶液中,硝酸盐的加入能够抑制不锈钢的电化学腐蚀,而草酸能够显著增强溶液对不锈钢的电化学腐蚀能力,在硝酸和草酸溶液体系中加入1g/L柠檬酸后,自腐蚀电流由6.02μA/cm~2上升到22.8μA/cm~2,对电流腐蚀有较明显的促进作用。     

不同pH值高锰酸钾对不锈钢腐蚀性能影响

采用重量法、扫描电子显微镜、动电位极化曲线法研究304L不锈钢在不同pH值高锰酸钾溶液中的腐蚀行为。304L不锈钢经过pH值为1.8的酸性高锰酸钾溶液(NP)氧化后表面腐蚀产物最多,pH值为6.5的高锰酸钾溶液(HP)氧化后表面腐蚀产物最少,pH值为12.5的碱性高锰酸钾溶液(AP)氧化后表面腐蚀产物居中。经过氧化步骤后,试样经过硝酸与抗坏血酸混合还原溶液清洗后都具有金属光泽,微观形貌区别不大。304L不锈钢在HP中的腐蚀电流密度最小,在NP和AP中的腐蚀电流密度大于HP。化学去污清洗工艺中高锰酸钾溶液对不锈钢的腐蚀性最弱,NP、AP对不锈钢基材的腐蚀性强于HP。     

316NG和321不锈钢在模拟海洋大气氛围中的电化学点蚀性能研究

利用电化学极化曲线和临界点蚀温度测量方法,对比研究316NG和321不锈钢在3.5%的Na Cl溶液中的抗点腐蚀性能。实验结果表明:所有测试温度下(室温、40℃、60℃、80℃)316NG的点蚀击穿电位(Eb)均显著高于321不锈钢;随着温度升高,316NG和321不锈钢的Eb显著下降,抗点蚀性能变差;3.5%Na Cl溶液中316NG和321不锈钢的临界点蚀温度(CPT)分别为20.1℃和3.9℃。从电化学角度看,在模拟海洋环境下,316NG的抗点蚀性能显著优于321不锈钢。扫描电镜下在321不锈钢的点蚀坑中观察到Ti N或Ti C颗粒存在,致使抗点蚀性能降低。     

压水堆条件下锌对奥氏体不锈钢腐蚀性能的影响

模拟压水堆一回路冷却剂环境,对316和304奥氏体不锈钢在不加锌和加锌浓度为50ppb的315℃溶液中进行了两组500h腐蚀实验。结果表明,锌能有效地降低两种材料的均匀腐蚀速率,加锌后表面氧化膜厚度变薄,氧化膜形貌和成分也有明显改变,304不锈钢表面有大量针状腐蚀产物出现。     

Ti35钛合金与低碳不锈钢在硝酸溶液中的电化学腐蚀对比研究

从电化学角度对Ti35合金(Ti-5%Ta)和超低碳不锈钢在硝酸溶液中的抗腐蚀性能进行了对比评价。对不同温度、不同浓度、不同添加离子等条件下的阳极极化曲线进行了测试。得到结论:在相同温度下,硝酸溶液浓度的变化导致了钛合金的腐蚀加剧。在相同浓度下,随着温度的升高,钛合金腐蚀越来越不明显。Cr6 离子浓度对钛合金腐蚀能力的影响不大。铀酰离子的作用较弱,加了铬和钌离子后表现出对阳极反应的明显抑制作用。通过表面微观形貌的观察,发现不锈钢对硝酸浓度的变化更为敏感,氧化性离子的综合作用对于不锈钢的耐蚀性影响很大。研究结果表明,Ti35合金具有比不锈钢优异得多的抗腐蚀性能,有希望取代000Cr25Ni20不锈钢而用于后处理设备。     

硝酸溶液中铝的电化学溶解行为

铝常用作核燃料的包壳材料以及辐照靶件的基体材料。研究其电化学溶解行为对于开发新型铝基体首端溶解工艺具有重要意义。研究了铝在硝酸中的阳极溶解电化学行为,并测定一系列条件下铝阳极的电化学阻抗谱、极化曲线和循环伏安曲线。结果表明:在稳态时,铝表面形成钝化膜,钝化膜的厚度随硝酸浓度的升高先下降后升高,在硝酸浓度为4mol/L时厚度较薄;体系的温度升高、硝酸铝浓度下降都使钝化膜的厚度减小;在有极化电流作用下,升高温度、增大酸度以及增大硝酸铝浓度,都易于使膜击穿,从而实现阳极溶解;铝在硝酸中的溶解速率仅与电流强度有关,电解速率可达0.4g/(A·h)。     

臭氧预处理方法在不锈钢去污过程中的应用

针对放射性污染的不锈钢钝化层难以去污的特点,首先模拟不锈钢钝化行为,然后利用臭氧的氧化性改变不锈钢钝化层结构,使放射性核素易于去除,从而提高去污效率。实验结果表明,304不锈钢在4mol/L硝酸钝化液中浸泡6h,可得平均厚度26μm的钝化层;利用7.47mg/L的臭氧水,对钝化后的不锈钢污染样片进行氧化120min,可使钝化膜消失;钝化的不锈钢模拟污染样片去污因子随着臭氧水浓度和氧化时间升高而升高,但超过一定时间会到达去污平台,去污因子不再上升。臭氧水的氧化作用可使去污剂的去污因子提高约7.7倍。     

Correlation between composition of passive layer and corrosion behavior of high Si-containing austenitic stainless steels in nitric acid

Austenitic stainless steels with 18% Cr have a good corrosion behavior in pure nitric acid. However, when oxidizing power of the solution increases, this kind of stainless steels faces a severe intergranular corrosion. Adding a sufficiently high concentration of silicon to the steel avoids this type of corrosion: in oxidizing solutions, those stainless steels exhibit generalized corrosion but their dissolution rate is higher than the one of stainless steels without silicon. To find out the role of silicon on such effects, the corrosion behavior of two different stainless steels with equivalent chromium content but with different silicon content (304L steel and Uranus S1N) has been studied in concentrated nitric acid solutions. Correlations have been evidenced between the passive layer composition investigated by XPS analysis and the corrosion behavior characterized by electrochemical techniques. The presence of silicon in the steel changes neither the oxidation state of chromium or iron, nor the ratio between iron and chromium in the passive layer. Silicon is present in the passive layer in an important content (35 at.%) and thus decreases the chromium content of the passive layer (80 and 50 at.% respectively for 304L steel and Uranus S1N after nitric passivation). Uranus S1N exhibits a less protective passive layer and so its generalized corrosion rate is higher than the one of 304L steel. A selective deposition of platinoïds highlights differences of polarization distribution on the surface between the grain boundaries and grain faces for theses steels. For Uranus S1N, the similar electrochemical behavior of grain boundaries and faces might be connected with the homogeneous silicon distribution.     

Effect of nitrate on corrosion of austenitic stainless steel in boiling nitric acid solution containing chromium ions

The oxidation behavior of chromium and the corrosion behavior of austenitic stainless steel in boiling nitric acid solution containing highly concentrated nitrates were investigated using UV-visible spectroscopic measurements, Raman spectral measurements, immersion tests, and potentiodynamic polarization measurements. The oxidation rate measurement of chromium from Cr(III) to Cr(VI) was performed by 1 M boiling nitric acid solution containing each highly concentrated nitrates: Al(NO₃)₃, Nd(NO₃)₃, Ca(NO₃)₂, Mg(NO₃)₂, and NaNO₃ as a simulant of uranium nitrate in uranium concentrator in reprocessing plants. As a result, the rate of chromium oxidation was different depending on the added nitrates even at the same nitric acid concentration. In addition, the oxidation rate of chromium was increased with increasing the calculated partial pressure of nitric acid in consideration of the hydration of cation of nitrates. Furthermore, the corrosion rate of type 310 stainless steel was accelerated by the solution having a high chromium oxidation rate containing nitrates. These results indicated that the acceleration of the corrosion rate in the solutions depending on the oxidation rate of chromium, and the rate is affected by the salt-effect of nitrates.     

中国实验快堆奥氏体不锈钢焊接件与钠蒸气的相容性

在400℃高温钠蒸气介质中,对俄罗斯进口的08X16H11M3奥氏体不锈钢中间热交换器与国产304奥氏体不锈钢支撑的焊接件进行了3000h的相容性模拟试验研究。结果表明：在本试验条件下,焊接试样的腐蚀速率很低,其等级为完全耐蚀;与钠蒸气接触的试样焊接区及热影响区表面均未观察到晶间腐蚀;在试验后试样的焊接区和热影响区表面,所有试样均未观察到Na的渗入;在国产304不锈钢热影响区的个别表面位置虽有1～2μm深的晶界小喇叭口出现,但其成分未出现异常;在试验过程中,国产304不锈钢表面出现明显的组分元素溶解扩散,但对材料基体的组织及力学性能未产生明显影响,试验后试样的抗拉强度、屈服强度和延伸率与试验前相比无明显差别,断口形貌与试验前一样仍呈韧性断裂特征。     

Investigation of the corrosion behavior of 304L and 316L stainless steels at high-temperature borated and lithiated water

The effects of temperature and dissolved oxygen on the electrochemical behavior and the oxide film formation of grades 304L and 316L stainless steels at high-temperature borated and lithiated water were investigated by means of potentiodynamic polarization, scanning electron microscopy and X-ray photoelectron spectroscopy. The results revealed that increasing the solution temperature degrades the passivity of the oxide films formed on both grades of steel and shifts their corrosion potential toward more negative potentials. The oxide films formed on the steel samples immersed into the solution containing 20 ppb dissolved oxygen (DO) showed a duplex structure, in which the inner layer was mostly a composition of Cr oxides and the outer layer mainly was a Fe oxide and Ni–Fe spinel. Only a single layer of Cr-rich oxide was observed in the oxide films formed in the solutions with the DO concentrations higher than 20 ppb. Higher amount of Cr in the oxide films formed on the type 316L compared to 304L improves the passivity of the oxide film of this grade of steel and results in a wider passive region in its potentiodynamic polarization curves.     

High corrosion resistant Ti-5%Ta-1.8%Nb alloy for fuel reprocessing application

The conventional low carbon austenitic stainless steels display good corrosion resistance behaviour in nitric acid media. However, they are sensitive to intergranular corrosion in boiling nitric acid media in the presence of oxidizing ions like hexavalent chromium, tetravalent iron and hexavalent plutonium. The Ti-5%Ta-1.8%Nb alloy was evaluated as a candidate material for such applications of nuclear fuel reprocessing. Extensive tests were carried out to establish the superior corrosion properties in comparison to the conventional stainless steel or nitric acid grade stainless steel. The fabricability of this new alloy to various shapes like rod, sheet, wire and its weldability, which is required for making vessels, was found to be good.     

Corrosion of stainless steels in lead-bismuth eutectic up to 600 °C

An experimental program has been carried out to understand the differences in the corrosion behaviour between different stainless steels: the austenitic steels 304L and 316L, the martensitic steels F82Hmod, T91 and EM10, and the low alloy steel P22. The influence of oxygen level in Pb-Bi, temperature and exposure time is studied. At 600 °C, the martensitic steels and the P22 steel exhibit thick oxide scales that grow with time, following a linear law for the wet environment and a parabolic law for the dry one. The austenitic stainless steels show a better corrosion behaviour, especially AISI 304L. Under reducing conditions, the steels exhibit dissolution, more severe for the austenitic stainless steels. At 450 °C, all the materials show an acceptable behaviour provided a sufficient oxygen level in the Pb-Bi. At reducing conditions, the martensitic steels and the P22 steel have a good corrosion resistance, while the austenitic steels exhibit already dissolution at the longer exposures.     

Stainless steel containers for the storage of low and medium level radioactive waste

Corrosion investigations have been performed on the austenitic structural steel AISI 304L, in comparison with the structural steel AISI 316L, in an aerated and a de-aerated solution, which was leached from low and medium level radioactive waste. On the basis of measured potentio-dynamic anodic polarization curves and the results of cyclic polarization tests, it was found that both types of steel, as well as the corresponding welds, had a high pitting potential and a high protective potential, which means that they have a strong tendency to form a compact and corrosion-resistant passive film. The repassivation capability of both types of steel prevents the occurrence of stress corrosion cracking at the level of concentration of chloride ions which corresponds to the described type of waste, whereas absorbed atomic hydrogen does not reduce toughness or cause hydrogen embrittlement. The results of the research work confirmed that it is possible to use AISI 304L structural steel for the construction of containers for the temporary, 30-year storage of low and medium level radioactive waste.