模拟草酸钚沉淀母液中草酸电解破坏研究

采用循环伏安法和线性扫描法对模拟草酸钚沉淀母液中草酸和钚的电化学行为进行研究。研究结果表明,HNO₃介质中的H₂C₂O₄在Pt电极上的氧化为不可逆反应。在模拟的草酸钚沉淀母液中,因Pu(Ⅳ)被C₂O^2-₄络合而未出现Pu(Ⅲ)/Pu(Ⅳ)的氧化还原峰,H₂C₂O₄的氧化峰则清晰可见,H₂C₂O₄的氧化反应仍为不可逆过程。对模拟草酸钚沉淀母液进行恒电流电解,考察了模拟母液中Pu(Ⅳ)初始浓度对草酸电解速率的影响以及电解过程中Pu价态的变化。结果表明,钚浓度为0.002～0.1g/L时,对H₂C₂O₄的电解速率影响不大。恒电流密度下电解可将草酸钚沉淀母液中草酸的浓度破坏到0.001mol/L以下,可满足工艺要求。     

HNO3介质中H2C2O4电解动力学及电解氧化机理

以Pt-Ti（镀铂钛）为阳极,Ti为阴极,对HNO₃介质中的H₂C₂O₄进行恒电流电解,考察HNO₃介质中H₂C₂O₄电解动力学特性及其影响因素,并初步探讨HNO₃介质中H₂C₂O₄的电解氧化机理。研究结果表明：电流密度控制在25～37mA/cm2、HNO₃浓度为2～3mol/L、温度为30~40℃时,电解效果最佳;微量金属离子（Fe^₃+、MnO-4、Ag+）的存在对H2C2O4的电解起催化作用,能较大提高电解速率;电解氧化法破坏H2C2O4的效率高于KMnO4蒸煮法,在工业中有潜在的应用前景。     

不锈钢表面钚污染的擦拭去污

为了防止污染范围扩大,减少对工作人员、公众和环境的辐射危害,需对钚污染的材料或设备进行去污。本工作分别采用不同种类去污试剂对滴加钚标准溶液后自然风干、加热烘干及浓盐酸腐蚀的三类不锈钢模拟污染样品进行擦拭去污实验。结果表明：盐酸及NaF+H₂C₂O₄+HNO₃两种去污试剂对自然风干的样品去污效率＞95%;5%的盐酸对加热烘干样品的去污效率约为95%;8%~10%的盐酸溶液、5%的硝酸溶液以及NaF+H₂C₂O₄+HNO₃对浓盐酸腐蚀样品的去污效率＞95%。     

氧化硼对铁磷酸盐玻璃陶瓷固化体的影响

研究了不同B₂O₃掺量对铁磷酸盐玻璃陶瓷高放废物固化体结构和性能的影响。应用溶出速率法（DR）对固化体进行了化学稳定性测试,使用傅里叶变换红外光谱（FTIR）和X射线衍射（XRD）方法研究了样品的结构。研究结果表明：玻璃陶瓷固化体的主晶相为独居石;B₂O₃的引入对玻璃陶瓷固化体的化学稳定性影响较大,以10%（摩尔分数）的B₂O₃代替Fe₂O₃制得的固化体化学稳定性最佳,其28d的质量浸出率约为7.81×10^-9g•cm^-2•min^-1;试样中存在大量正磷酸基团［PO₄］^3-和少量焦磷酸基团［P₂O₇］^4-,无偏磷酸基团［PO₃］^-存在,固化体中的B主要以［BO₄］四面体基团形式存在。     

八氧化三铀粉末制备与利用

本工作研究U₃O₈粉末制备工艺流程和工艺参数，测试制备出的U₃O₈粉末的物化性能以及U₃O₈粉末添加对UO₂芯块产品质量的影响。分析结果表明：所制备的U₃O₈粉末可加到UO₂粉末中而被回收利用；控制U₃O₈粉末加入量，可调节UO₂芯块的密度和微观组织，制备出合格的UO₂芯块，从而提高了金属铀的直收率和利用率。     

离子交换色谱中硼同位素交换反应平衡常数的理论预测

外部溶液相中B(OH)₃与离子交换树脂相中B(OH)₄^-、B₃O₃(OH)₅^2-、B₃O₃(OH)₄^-之间所发生的同位素交换反应的平衡常数K是离子交换色谱法分离硼同位素研究中的基本参数之一,但难以用实验手段精确测定。本研究利用密度泛函理论（DFT）在B3LYP/6—31G理论水平上计算了气态下B(OH)₃、B(OH)₄^-等的振动频率,用计算得到的频率,基于Urey模型求得B(OH)₃、B(OH)₄^-、B₃O₃(OH)₅^2-、B₃O₃(OH)₄^-的简约配分函数比（RPFR）,进而得到同位素交换反应平衡常数。结果表明,B(OH)₃和B(OH)₄^-间的同位素效应显著,其平衡常数K在25 ℃时为1.025 7,B(OH)₃与B₃O₃(OH)₅^2-和B₃O₃(OH)₄^-反应的平衡常数较小,分别约为1.017 2和1.008 4。     

人造岩石固化掺铀模拟放射性焚烧灰

以天然锆英石、模拟放射性焚烧灰、CaCO₃、TiO₂、UO₂为原料,采用高温固相反应,对人造岩石固化掺铀模拟放射性焚烧灰进行研究。借助XRD、SEM、抗浸出性能测试等分析测试方法,研究固化体的性能。结果表明：在空气气氛下烧结,固化体的晶相为CaZrTi₂O₇［Ca（Zr,U）Ti₂O₇］、CaTiSiO₅、CaTiO₃和CaUO₄,一部分U固溶于Ca（Zr,U）Ti₂O₇中;较多CaZrTi₂O₇的生成有利于Ca（Zr,U）Ti₂O₇固溶更多的U;模拟放射性焚烧灰掺量为60%、UO₂含量为6.88%的人造岩石固化体,1～35d铀的归一化浸出率为0.17~2.81μg/(cm²•d),42～192d铀的归一化浸出率为0.09～0.13μg/(cm²•d)。     

C-276合金在650℃/25MPa超临界水中的腐蚀行为

研究了HastelloyC-276（C-276）镍基合金在650℃/25MPa超临界水中的腐蚀特性。采用扫描电镜、X射线能谱仪、X射线衍射和X射线光电子能谱分析了氧化膜的腐蚀形貌、组织结构和合金元素分布。研究结果表明,C-276合金在650℃/25MPa的超临界水中的腐蚀过程主要是Ni的溶解,由于不能形成均匀、完整的氧化膜,合金在超临界水中并不具备优越的耐腐蚀性能,其双层结构的氧化膜富Cr而贫Ni、Mo,外层疏松的大颗粒（Ni(OH)₂和NiO）为金属溶解和氧化物沉淀形成,内层（Cr₂O₃）的生长则是水穿过氧化物微孔作用的结果。     

金属铀表面氧化动力学的X射线衍射研究

利用X射线衍射和Rietveld方法研究室温～150℃和300℃下金属铀表面氧化，对氧化过程中试样的表面结构以及氧化动力学进行分析。将试样表面氧化物随时间的变化作定量计算，绘制出不同温度下金属铀表面的氧化动力学曲线，对50～150℃范围内的氧化动力学数据进行拟合，获得不同温度下的氧化反应速率常数，由此得到大气环境下金属铀表面形成UO₂的活化能为46.0kJ/mol。在300℃下，氧化产物U₃O₈逐渐在UO₂上形成，其形成过程符合成核生长机理。     

静电场激励液-液体系相间铜反萃传质特性

在改进的传质池中通过在线检测草酸浓度,应用瞬时传质系数与平均传质系数,研究了各种方向及组合、不同电压、电极板形状与面积等条件下静电场对体系Cu²⁺-HDEHP-CCl₄/H₂O-H₂C₂O₄伴随生成CuC₂O₄的传质过程特性。外场电压变化、电极面积可改变相间的传质速率,与传质方向成45°夹角的静电场作用对相界面传质速率的影响更为显著,表明相间传质阻力结构或相间传质层具有各向异性。     

奥氏体ODS钢在超临界水中的腐蚀行为

研究了奥氏体ODS钢（316-ODS）在600 ℃/25 MPa超临界水（SCW）中的腐蚀特性。采用腐蚀增重法、SEM、EDS和XRD分析了材料的氧化动力学、氧化膜的形貌、合金元素分布和组织结构。研究结果表明,316-ODS钢在SCW中出现了疖状腐蚀,同时还出现了敏化,其腐蚀增重服从幂指数生长规律。316-ODS钢表面氧化膜为双层结构,内层氧化膜富Cr贫Fe,其主要成分为FeCr₂O₄,而外层氧化膜富Fe贫Cr,其主要成分为Fe₃O₄。     

AP1000一回路氧化膜特性研究

AP1000与一般压水堆不同的是其一回路采用注锌加氢技术,使其一回路氧化膜特性发生变化。试验在高压釜中模拟AP1000一回路水化学工况,研究F304L、F316、690三种反应堆主工艺设备材料表面生成的氧化膜特性。结果表明,氧化膜为双层结构,外层氧化膜成分主要是Fe₂O₃及Fe₃O₄。F304L不锈钢与F316不锈钢内层氧化膜主要是ZnCr₂O₄,注入的Zn元素取代了FeCr₂O₄中的铁元素,形成了致密的ZnCr₂O₄ 氧化层,内层氧化膜存在少量ZnO和ZnFe₂O₄。690合金的氧化膜内层为ZnCr₂O₄,同时存在较高含量的ZnO和ZnFe₂O₄。与前两者不同的是,690合金的氧化膜含少量的二价镍,以NiFe₂O₄和NiCr₂O₄形式存在。加锌加氢使得氧化膜更加致密,也明显变薄。     

304NG在超临界水中腐蚀后氧化膜分析

研究了奥氏体不锈钢304NG(以下简称304NG)在压力为25 MPa,温度分别为500、550、600、650℃超临界水中的腐蚀行为,通过扫描电镜-电子能谱(SEM-EDX)、X射线衍射(XRD)对304NG试样氧化膜微观组织的研究表明:304NG在超临界水中腐蚀后,表面氧化膜由岛状和非岛状2种不同形貌的腐蚀相组成.其中,含岛状腐蚀相的氧化膜具有双层结构,外层为Fe3O4相,内层为Fe3O4和FeCr2O4相;不含岛状腐蚀相的氧化膜为单层结构,氧化膜中含有Fe3O4和FeCr2O4相.同时,304NG在超临界水中氧化膜存在脱落现象,氧化膜脱落程度随温度升高而加剧.     

Microstructural analysis and XPS investigation of nodular oxides formed on Zircaloy-4

In order to study nodular oxidation behavior under LOCA conditions, Zircaloy-4 cladding tubes were oxidized in high-temperature steam ambience and the growth evolution and microstructural properties of the oxides formed on the Zircaloy-4 surfaces were then investigated. Optical metallography showed different growth behaviors of uniform black oxide and localized whitish nodular oxide. The changes in composition and chemical states of the oxides formed on the Zircaloy-4 surface were investigated using X-ray photoelectron spectroscopy (XPS). Anion-deficient and non-stoichiometric ZrO was the main species in initial black uniform oxide surface, while stoichiometric ZrO₂ was the main oxide species in the whitish nodular oxide. A stoichiometric composition in the nodular oxide resulted in a decrease in plasticity of the oxide layers. Unlike black uniform oxide, XPS spectrum from the nodular oxide showed clear Sn photopeak, which indicates that Sn species were observed in the nodular oxide only. As a result, it is concluded that the decreased plasticity and localized Sn additives may be the causes of nodular oxide initiation under LOCA conditions.     

Plasma-Assisted Chemical Vapor Deposition of Titanium Oxide Films by Dielectric Barrier Discharge in TiCl_4/O_2/N_2 Gas Mixtures

Low-pressure dielectric barrier discharge（DBD） TiCl4/O2and N2 plasmas have been used to deposit titanium oxide films at different power supply driving frequencies. A homemade large area low pressure DBD reactor was applied, characterized by the simplicity of the experimental set-up and a low consumption of feed gas and electric power, as well as being easy to operate. Atomic force microscopy, scanning electron microscopy, energy dispersive spectroscopy,and contact angle measurements have been used to characterize the deposited films. Experimental results show all deposited films are uniform and hydrophilic with a contact angle of about 15 o.Compared to titanium oxide films deposited in TiCl4/O2gas mixtures, those in TiCl4/O2/N2gas mixtures are much more stable. The contact angle of titanium oxide films in TiCl4/O2/N2gas mixtures with the addition of 50% N2 and 20% TiCl4 is still smaller than 20 o, while that of undoped titanium oxide films is larger than 64 owhen they are measured after one week. The low-pressure TiCl4/O2plasmas consist of pulsed glow-like discharges with peak widths of several microseconds, which leads to the uniform deposition of titanium oxide films. Increasing a film thickness over several hundreds of nm leads to the film’s fragmentation due to the over-high film stress. Optical emission spectra（OES） of TiCl4/O2DBD plasmas at various power supply driving frequencies are presented.     

HR3C在超临界水中的腐蚀性能研究

通过高压釜浸泡实验研究了超级奥氏体不锈钢HR3C在循环的超临界水（SCW）中的均匀腐蚀性能,实验温度分别为550、600、650 ℃,压力为25 MPa,并对实验后试样生成的氧化膜进行了SEM、EDS和XRD分析。实验结果显示,HR3C在SCW环境中的氧化腐蚀速率随着温度的升高而增大,1 500 h后650 ℃ SCW环境下材料的腐蚀增重约为550 ℃时的2倍。材料表面生成的氧化膜主要成分为FeCr₂O₃、Fe₃O₄和Fe₂O₃,内层氧化膜富Cr而外层氧化膜富Fe。     

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。     

Conversion of NO with a catalytic packed-bed dielectric barrier discharge reactor

This paper discusses the conversion of nitric oxide (NO) with a low-temperature plasma induced by a catalytic packed-bed dielectric barrier discharge (DBD) reactor.Alumina oxide (Al2O3),glass (SiO2) and zirconium oxide (ZrO2),three different spherical packed materials of the same size,were each present in the DBD reactor.The NO conversion under varying input voltage and specific energy density,and the effects of catalysts (titanium dioxide (TiO2) and manganese oxide (MnOx) coated on Al2O3) on NO conversion were investigated.The experimental results showed that NO conversion was greatly enhanced in the presence of packed materials in the reactor,and the catalytic packed bed of MnOx/Al2O3 showed better performance than that of TiO2/Al2O3.The surface and crystal structures of the materials and catalysts were characterized through scanning electron microscopy analysis.The final products were clearly observed by a Fourier transform infrared spectrometer and provided a better understanding of NO conversion.     

Measurements of hydrogen permeation and absorption in zirconium oxide scales

The hydrogen absorption and the permeation behavior through the oxide layer formed on modified Zircaloy-4 (Zry-4) alloys were investigated. The modified Zry-4 was prepared by altering the chemical composition of standard Zry-4. The tin content of Zry-4 (1.5 wt%) was reduced to 0.5 wt%, and alloying elements Si, O and Nb were added from 0.01 to 0.2 wt%. The oxide layers were grown in a static autoclave at 360 °C under 18.3 MPa for 150 days. Fick’s law was used to calculate the diffusivity of hydrogen after the steady state of the permeation flux was reached. The diffusivity of hydrogen in the 0.5Sn–0.1Nb–0.1Fe–0.2Cr–0.2O–Zr specimen was lower than that in the 1.5Sn–0.2Fe–0.1Cr–0.1O–0.01Si–Zr and Zry-4 specimens. As the area fraction of precipitates increased, the hydrogen diffusivity increased whereas an inverse relationship between the diffusivity and the amount of the tetragonal phase was observed. In addition to the oxide structural study, the effects of the microstructure of the zirconium alloys such as precipitates and grain boundaries on the hydrogen absorption were studied.     

Microstructural Characterization of SCC Crack Tip and Oxide Film for SUS 316 Stainless Steel in Simulated PWR Primary Water at 320°C

Recent studies on stress corrosion cracking (SCC) behaviors of austenitic stainless steels in hydrogenated high-temperature water show that low potential SCC (LPSCC) can occur on cold-worked SUS 316 stainless steel (hereinafter, 316SS). In this study, oxide films and crack tips on cold-worked 316SS exposed to hydrogenated high-temperature water were characterized using analytical transmission electron microscopy (ATEM), grazing incidence X-ray diffraction (GIXRD) and Auger electron spectroscopy (AES) in order to study the corrosion and SCC behaviors of these films and crack tips. A double layer structure was identified for the oxide film after a constant extension rate tensile (CERT) test. The outer layer was composed of large particles (0.2–3 μm) of Fe₃O₄ and the inner layer consisted mainly of fine particles (~10 nm) of FeCr₂O₄. In addition, nickel enrichment was identified at the metal/oxide interface. Particles of Fe₃O₄ were also identified on the crack walls. These results indicate that the same electrochemical reactions had occurred inside and outside the crack. The crack tip area was filled with corrosion products of a chromium-rich oxide. In addition, nickel enrichment was observed at the crack tip. The formation of the nickel-enriched phase indicates that a selective dissolution reaction of iron and chromium occurred at the front of the LPSCC crack.