氘代氨的制备及其稳定性

制备氘代氨可采用同位素交换、直接催化合成以及由氮化镁和重水反应等方法。为了获得同位素丰度很高的氘代氨,我们参照文献[1—4],改进了某些操作,首先制备氮化镁,然后在一套玻璃系统内使氮化镁与重水反应。此方法可用于实验室制备少量示踪研究用氘代氨。此外,利用红外吸收光谱,我们还研究了氘代氨在某些含氢化合物存在下的稳定性。     

离子注入碳对铀表面初始氧化行为影响的研究

用俄歇电子能谱(AES)分别对高真空室中铀样品及多能量叠加离子注入碳铀样品与氧气吸附及初始氧化过程进行了研究.结果表明,在高真空室中,清洁铀表面很容易吸附氧化,发生氧化反应,当O2暴露剂量为40 L时,清洁铀表面就会形成一层UO2;离子注入碳后铀表面的抗氧化能力增强.     

高产率自动化合成2-18F-2-脱氧-D-葡萄糖

研究了2-18F-2-脱氧-D-葡萄糖(18F-FDG)的高产率自动化合成工艺.以三氟甘露糖为前体,采用"一锅法"和TRACERlab FXF-N自动化合成装置,在同一反应瓶中进行亲核氟化、氢氧化钠水解两步反应,然后用小柱中和分离纯化制备了18F-FDG注射液.18F-FDG的总合成时间约24 min,未经校正的放化产率约为60%,放化纯度大于99%.采用改进了的自动化工艺合成18F-FDG注射液,操作简便,可望成为18F-FDG较为实用的合成方法.     

高分子量叠氮缩水甘油醚聚合物的合成研究

为了提高以叠氮缩水甘油醚聚合物(GAP)为粘结剂的塑料粘结炸药(PBX)和推进剂的能量并改善其力学性能,合成了高分子量GAP(HGAP),重均分子量(M_w)达150021,叠氮化率99.16％。通过对催化剂、抗氧剂,氮气保护、投料比和反应温度等因素对聚环氧氯丙烷(PECH)叠氮反应影响的分析和研究,得到了制备高叠氮率,高分子     

离子轰击对氮化铀表面氧化行为的影响

采用离子氮化技术制备得到一定厚度的氮化铀层,以不同能量的氩离子轰击考察氮化铀的辐照氧化行为,并与大气中的自然氧化行为进行对比,考察材料在辐照环境下的稳定性。结果表明,氮化铀表面经氩离子轰击后,表面形貌发生了改变;氩离子轰击氧化与大气中的自然氧化行为存在差异,离子轰击增强了氮化铀表面的氧化程度,但其对氧化行为的影响主要在浅表面,大气氧化的氮化铀氧化层更厚;随着氩离子轰击能量的增加,表面氧化物含量及氧化层深度显著增加。总体而言,氩离子辐照对氮化铀层的影响随深度的增加而减弱,并不影响氮化铀的整体稳定性。     

简便、快速自动化合成肿瘤显像剂18F-氟代乙酸盐和1-H-1-(3-18F-2-羟基丙基)-2-18F-硝基咪唑

用"一锅法"和TRACERlab FXF-N自动化合成仪系统合成了18F-氟代乙酸盐(18F-FAC)和1-H-1-(3-18F-2-羟基丙基)-2-硝基咪唑(18F-FMISO).以溴代乙酸苄酯为前体,在同一反应瓶中经亲核氟化、NaOH水解两步反应及Sep Pak小柱分离纯化制备了18F-FAC注射液,总合成时间小于40 min,未经校正的放化产率和放化纯度分别大于45%和99%.以1-(2'-硝基-1'-咪唑基)-2-O-四氢吡喃基-3-O-甲苯磺酰基丙二醇为原料,用类似方法制备了18F-FMISO注射液,总合成时间小于40min,未经校正的放化产率和放化纯度分别大于40%和95%.采用"一锅法"自动化合成18F-FAC和18F-FMISO注射液,操作简便,该工艺可用制备2-18F-2-脱氧-D-葡萄糖(18F-FDG)的全自动化合成模块来制备18F-FAC和18F-FMISO注射液.     

CCl_(4)和HCl气体氯化铀氧化物北大核心CSCD

分别以CCl_(4)和HCl气体作为氯化试剂,进行了铀氧化物(主要为U_(3)O_(8))的氯化机理和各影响因素研究。以CCl_(4)为氯化试剂对U_(3)O_(8)粉末进行氯化,通过热重分析研究了氯化反应过程的机理及动力学行为,氯化产物主要为UCl_(4)。同时研究了CCl_(4)对不同种类和形态铀氧化物的氯化,UO_(2)芯块由于结构致密很难进行氯化,UO_(2)粉末和UO_(3)粉末很容易被CCl_(4)氯化,产物分别为UCl_(4)和UCl_(6)。以HCl气体为氯化试剂对LiCl-KCl熔盐中的U_(3)O_(8)粉末进行氯化,研究了反应温度、氯化时间、HCl气体流速、U_(3)O_(8)粉末投料量以及铀氧化物种类和形态的影响。结果表明,提高反应温度、延长反应时间、提高HCl气体流速,有利于氯化率的提高。推荐HCl气体氯化U_(3)O_(8)粉末的工艺参数为:氯化反应温度为500℃、HCl气体流速为0.6 L/min。     

电沉积铀靶制备技术研究

研究了在水溶液体系中采用电沉积法制备铀靶的方法。以0.15mol/L草酸铵为电解液,铂丝为电极,通过考察阴极处理工艺、电流密度、电沉积时间、pH、温度、搅拌速度、镀液中UO2(NO3)2浓度等对电沉积效率及镀层质量的影响,确定了制备电沉积铀靶的最佳工艺参数,其中,沉积效率通过紫外分光光度法测得。在pH=2～3、电流密度60mA/cm2、保持温度60℃、镀液中UO2(NO3)2浓度约1.67mg/mL时沉积效率可达约98%。采用红外光谱、X射线能谱和扫描电镜等对铀沉积层进行了测试。结果显示,铀以水合聚合物的形式存在,可能的结构为[UO2(H2O)4-O-UO2(H2O)4-O],铀的沉积层的纯度较高,除检测到铀(65.35%)、氧(27.38%)、碳(5.46%)和铂(1.81%)外未引入其他杂质,镀层表面平整、致密,与衬底结合牢固。单次铀的电沉积层厚度可达6mg/cm2,采用高温烧结后重复电镀的方法可将电沉积铀的密度提高到6～8mg/cm2。     

辉光等离子体氮化铀表面的氢腐蚀

采用辉光等离子体氮化方法制备铀表面氮化样品。俄歇电子能谱和X射线衍射对样品的分析表明,铀表面形成了厚约250 nm、主要成分为α-U₂N_3+x的氮化层,氮化层与基体之间具有平缓的过渡层,且氮在金属铀的基体内有一定扩散。与轻微氧化样品氢腐蚀的对比实验表明,氮化处理使样品表面缺陷密度减少,改性层对氢吸附、扩散有阻挡作用,氢蚀形核较慢且其生长明显受到改性层的抑制,这表明铀表面辉光等离子体氮化可作为延缓氢腐蚀的有效手段。     

共沉淀法制备(Th,U)O_(2+x)粉末工艺研究

采用共沉淀工艺制得钍铀共沉淀物(AUTh C),AUTh C经分解还原得到(Th,U)O2+x粉末。采用差热-热重分析仪分析AUTh C分解过程,多分子层吸附理论(BET)法测定(Th,U)O2+x粉末比表面积。研究p H值、氨水加入量等共沉淀反应条件对钍铀共沉淀反应影响,以及无水乙醇处理AUTh C对(Th,U)O2+x粉末比表面积影响。实验结果表明:缓慢加入碳酸铵使p H值为5.5时,钍铀均具有较高沉淀率。加入氨水使p H升至7.5以上时,能明显提高钍铀共沉淀性能,母液中残余铀浓度为89 mg/L,残余钍浓度为105 mg/L。使用无水乙醇处理AUTh C能防止分解过程中(Th,U)O2+x粉末出现硬团聚;分解终点温度为600℃下保温2 h,(Th,U)O2+x粉末比表面积达15 m2/g。     

Preparation of High Density Uranium Nitride and Uranium Carbonitride Fuel Pellets

Uranium nitride and uranium carbonitride fuel pellets were prepared for irradiation in the Japan Material Testing Reactor. The pellets are 6.9 mm in diameter and 7 mm long, and are of natural and 5% enriched uranium. Uranium nitride powder was prepared from uranium metal via hydride and higher nitride. Uranium carbide powder was prepared from uranium metal by hydriding and then reacting with propane. The lowest possible reaction temperatures were selected to obtain fine and reactive powders. Uranium nitride and mixed powders of different ratios (UC: UN = 1: 3, 1:1 and 3: 1) were cold pressed without binder. Sintering was carried out in a tungsten crucible in vacuum (10~⁴ mmHg) for 2 hr at 1,900°–2,000°C. The density of the pellets obtained was in the range of 90~95% of the theoretical value with an oxygen content of 1,300~2,100 ppm. No second phase, such as metallic uranium, were observed in the specimens, either by metallography or X-ray diffraction. These pellets of unexpectedly high density without second phase must have been obtained thanks to the good powder characteristics combined with proper sintering conditions. The compositions of uranium carbonitride pellets were found to be slightly nitrogen deficient, compared with the reactants.     

Nitration by a simulated fuel technique for nitride fuel re-fabrication

Nitration reaction of a spent nuclear oxide fuel through a carbothermic reduction and the change in thermal conductivity of the resultant nitride specimens were investigated by a simulated fuel technique for use in nitride fuel re-fabrication from spent oxide fuel. The simulated spent oxide fuel was formed by compacting and sintering a powder mixture of UO₂ and stable oxide fission product impurities. It was pulverized by a 3-cycle successive oxidation-reduction treatment and converted into nitride pellet specimens through the carbothermic reduction. The rate of the nitration reaction of the simulated spent oxide fuel was decreased due to the fission product impurities when compared with pure uranium dioxide. The amount of Ba and Sr in the simulated spent oxide fuel was considerably reduced after the nitride fuel re-fabrication. The thermal conductivity of the nitride pellet specimen in the range 295-373 K was lower than that of the pure uranium nitride but higher than the simulated spent oxide fuel containing fission product impurities.     

Effects of UO2/Zircaloy-4 Mole Ratios on Reaction of UO2 Fuel with Molten Zircaloy-4

Dissolution of UO₂ crucibles by molten Zircaloy-4 (Zry) was investigated in the temperature range of 2,223-2,373 K and for specimens having UO₂/Zry mole ratios between 7 and 18.2. The uranium concentration in the Zry melt rapidly increased during initial reaction time and approached saturated values, depending on reaction temperature and UO₂/Zry mole ratio. Kinetics of uranium concentration increase in the melt was analyzed based on a natural convection mass transfer model that takes into account the change of contact surface area/melt volume ratio with reaction time. The saturated uranium concentration in the Zry melt was inversely proportional to the U0₂/Zry mole ratio. An empirical correlation of saturated uranium concentration in the Zry melt was obtained as a function of UO₂/Zry mole ratios and reaction temperature. This study of the empirical correlation was intended to estimate maximum UO₂ fuel dissolution by molten Zry cladding during severe fuel damage accidents for three different reactor type fuels.     

Preparation of Ultra—fine Aluminum Nitride in Thermal Plasma

Ultra-fine aluminum nitride has been synthesized by the evaporation of aluminum powder at atmospheric-pressure nitrogen plasma in a hot-wall reactor.The average size of aluminum nitride particle is 0.11μm measured by scanning electric mirror(SEM),and the purity is at least over90% evaluated by X-Ray diffraction(XRD).The conversion of Al powder to aluminum nitride is strongly depended on the injection of NH3.Typical experimental parameters such as the feed rate of raw material,the flow rate of ammonia and the position of injecting aluminum powder into the reactor are given.     

Preparation of Uranium Nitrides from Uranium Tetrachloride

A study was made of UN preparation by two-step reactions with UCl₄, Al and N₂ gas. In the first step, an intermediate uranium nitride with an N/U ratio of 1.68 resulted from the reaction of UCl₄ with A1 under constant flow of N₂ at reaction temperatures higher than 800°C. The X-ray pattern of the intermediate nitride did not correspond to any previously known uranium nitride. A maximum conversion efficiency of about 70% was obtained at temperatures between 800° and 1,000°G for the first reaction. In the second reaction, the intermediate nitride was heat treated under vacuum. To obtain single phase UN from the intermediate nitride, the heat treatment required a temperature of at least 1,100°C, at which the minimum holding time was 60 min.     

二氧化铀粉末513K下空气氧化机制和动力学研究

为获取壳层O/U比约为2.25而芯部仍为UO₂的预氧化活性粉末以进行UO₂芯块的低温烧结试验,研究了UO₂粉末在513 K下于静态空气中的氧化机制和动力学。结果表明：UO₂粉末在513 K下氧化,可分为氧化前期和氧化后期;UO₂粉末氧化后期绝对增重比率极限为0.489%;氧化前期反应速率受界面化学反应控制,氧化后期反应速率受扩散控制;氧化前期,UO₂粉末氧化属于缩核模型,UO₂单颗粒单位面积上氧化质量的增加量解析式为Dw/Sn＝0.104 1t－2.146 67,氧化速率常数k_c＝3.49×10⁶exp(－73 919.39/RT)。     

CO对金属铀表面氧化层影响研究

用Ｘ射线光电子能谱（ＸＰＳ）和气相色谱（ＧＣ）分析研究了ＣＯ对金属铀表面氧化层的影响。ＣＯ在表面氧化层上的吸附反应导致了Ｕ４ｆ峰向低结合能方向位移，氧化物中氧含量减少，原子比（Ｏ／Ｕ）比值下降了７．２％。体系中ＣＯ２体积分数增大１１．０％。研究结果表明，ＣＯ气氛可抑制金属铀表面的进一步氧化。     

Carbothermic Synthesis of High Purity Plutonium Nitride from Plutonium Oxide

Synthetic conditions of PuN from carbothermic reduction of PuO₂ has been studied in a mixed 8%H₂+92%N₂ stream at a temperature range of 1,270–1,680°C. In the course of both reactions of the carbothermic synthesis of PuN from PuO₂ and the hydrogenation of C, the vaporization loss of Pu was observed. It increased with temperature in the temperature range of 1,350–1,450°C, and reached to a constant value 1.3% of total Pu in the temperature range of 1,450–1,680°C, at which PuN was synthesized at a reaction rate of high enough. The minimum mixing ratio (C/PuO₂, mole ratio) for the formation of high purity PuN depends on temperature. The value is 2.15 for 1,620°C and 2.35 for 1,680°C. The oxygen and carbon impurities in the PuN obtained were found to be 0.095–0.028 and 0.17–0.012w/0, respectively.     

加速器质谱法测量含铀微粒中铀同位素比的方法研究

准确测定含铀微粒同位素比在核保障中有重要的应用价值。本文采用将含铀微粒溶解并加入高纯Fe粉烘干的方法制样,采用中国原子能科学研究院的HI-13串列加速器质谱测量靶样中的同位素比。通过对CRM铀系列同位素标准样品的分析表明,该方法可测定高于10^-5的²³⁶U/²³⁸U同位素比;对于²³⁵U/²³⁸U同位素比在10^-4～10^-1范围内的含铀微粒,²³⁵U/²³⁸U同位素比相对扩展不确定度均小于10%。