磁助捕集分离制样/X射线荧光测量微量Tc

建立了磁助捕集分离制样(MASP)/X射线荧光分析微量Tc的方法,使用磁化树脂作为固相捕集剂捕集溶液中的锝,利用外加磁场快速分离制样,实现捕集、分离及制样同时完成,可直接使用X射线荧光测量样品Tc含量。研究并分析了反应时间、磁化树脂用量、液相体积及酸度等因素对测量的影响,给出了推荐测量分析流程。使用磁助捕集分离制样,对Tc的检出限为0.33mg/L,满足PUREX流程1AW工艺点测量Tc的要求。     

磁化TEVA树脂的制备及其表征

磁助制样可有效降低X射线荧光光谱（XRF）方法的检出限，该制样方法的核心是制备磁性分离材料。本工作使用共沉淀磁化的方法制备磁化TEVA树脂作为磁性分离材料。该材料可用于磁助制样/XRF分析后处理样品中的微量锝。通过扫描电镜、X射线衍射（XRD）、红外等分析手段对磁化TEVA树脂进行表征，结果显示磁化树脂中铁氧化物以物理镶嵌的方式与TEVA树脂相结合，其主要成分为纳米四氧化三铁。制得的磁化TEVA树脂既保留了TEVA树脂在低酸下对TcO₄^-选择性吸附的性能，又具有顺磁性，可用于磁助制样/XRF分析方法。该制备方法重复性好，制得的磁化树脂性能稳定、良好，用于磁助制样时制样回收率大于99%，可有效降低方法的检出限。     

^237Np（Ⅴ，Ⅵ）与其子体^233Pa的分离测定

通过对达到237Np-233Pa母子体平衡的多个样品液闪测量与低能γ测量的比较,求出了29、86、312keV处γ能谱的探测效率,同时确立了求算溶液中Np、Pa含量的计算方法,用以计算不同价态Np、Pa的分离效果。原始Np溶液为Np（V）,又用H2O2法制备了Np（Ⅴ）以作对比。分别用K2Cr2O7法、浓HNO3法制备了Np（Ⅵ）,通过TTA或TOPO萃取,再用不同反萃剂反萃的办法尝试分离Np（Ⅴ）、Np（Ⅵ）和 Pa。 实验结果表明:对于原始Np（Ⅴ）溶液,TTA或TOPO萃取能实现Np、Pa分离,镎在水相。而镤在有机相;萃取到TTA有机相中的大部分Pa可用含H2O2的反萃剂反萃到水相,TOPO有     

氨基羟基脲反萃TBP中的Np(Ⅳ)

为有效提高铀中除镎的分离效果,对氨基羟基脲反萃30%TBP-煤油中Np(Ⅳ)的性能进行了研究,探讨了反萃剂浓度、酸度、温度、反萃时间、相比、有机相铀浓度对Np(Ⅳ)反萃率的影响。单级研究结果表明,氨基羟基脲能有效反萃TBP中Np(Ⅳ)。使用氨基羟基脲为反萃剂的台架实验结果表明,6级反萃对1BU中Np的净化系数为20。     

固相萃取片法分析土壤中的~(99)Tc

系统研究了阴离子固相萃取片分离水溶液中TcO-4的性能,包括流速、酸度、体积、土壤基质对吸附的影响。在此基础上,针对土壤中99 Tc含量的分析,建立了以固相萃取片法为主要分离手段、液闪为放射性测量方法的分析流程,并利用模拟99 Tc污染土壤样品对分析流程进行了检验。研究结果表明,土壤中含有的本底放射性核素及常见沾污核素137 Cs、90 Sr-90 Y和天然铀对分析流程均无明显干扰,全流程99 Tc的化学收率在95%以上。样品质量为10g、液闪测量能量范围本底计数率为10min-1、测量时间为10h时,方法的最小可探测浓度约为0.07min-1·g-1,即1.1Bq/kg。     

温度对Np在北山花岗岩上吸附行为的影响

采用批式实验法研究了低氧条件下,温度对Np(Ⅳ)、Np(Ⅴ)在磁分离后的花岗岩和北山花岗岩上吸附行为的影响.测定了30、45、60、80℃下Np(Ⅳ)、Np(Ⅴ)在磁分离后的花岗岩和北山花岗岩上吸附的Kd值.研究发现,温度升高有利于Np(Ⅳ)、Np(Ⅴ)在花岗岩上的吸附;在近中性地下水体系中,Np(Ⅴ)较Np(Ⅳ)更易...     

普雷克斯流程中Np的行为和控制

在后处理流程的众多化学分离中 ,Np的走向和控制是国际后处理界关注的重点研究课题。根据我国和其他国家的研究成果 ,综合分析了后处理中Np的走向和控制。Np在辐照燃料溶解液中的价态分布主要取决于溶解液中HNO3与HNO2 之比 ,通常情况下 ,溶解液中Np(Ⅴ )占主要份额 ;Np在共去污阶段的走向有两种可能 ,一是将Np控制为Np(Ⅴ ) ,使其进入高放废液 (1AW ) ,二是将Np控制为Np(Ⅵ ) ,则Np将与U ,Pu一起进入有机相 ,但两者至今为止都难以实现定量分离。Np在U/Pu分离阶段部分随U ,部分随Pu。在U纯化循环中 ,理想的方法是采用低酸加热氧化Np(Ⅳ )至Np(Ⅴ ) ,以实现与铀的有效分离。     

硝酸肼还原反萃取分离镎/钚的研究

镎的提取和分离是国际后处理领域重点关注的研究课题之一。在Purex流程中,硝酸肼常被用来作为亚硝酸的清扫剂,此外,由于硝酸肼对Np(VI)和Pu(IV)的氧化还原反应具有选择性,理论上可以利用其反应速率上的差异来实现镎与铀钚的分离。为探索硝酸肼分离镎/钚工艺提供可行性,本文采用单级萃取设备研究了硝酸肼还原反萃Np和Pu的过程。通过研究硝酸浓度、硝酸肼浓度和反应温度对还原反萃过程的影响,确定了Np(VI)和Pu(IV)反萃动力学方程和表现活化能。进一步通过动力学方程得出硝酸肼还原反萃Np(VI)和Pu(IV)的半反应时间,并对Np(VI)/Pu(IV)分离过程的工艺进行了初步探索。     

用萃取色层法分离Np(Ⅳ),NP(Ⅴ)和Np(Ⅵ)

本文研究了用磷酸三(2—乙基己基)酯(以下简称为TIOP)作固定相、硝酸等为流动相的萃取色层法在分离Np(Ⅳ)、Np(Ⅴ)和Np(Ⅵ)中的应用。利用Np(Ⅳ)、Np(Ⅴ)和Np(Ⅵ)在TIOP—硅胶柱上分配系数的差异使不同价态的镎得到分离。Np(Ⅴ)不被TIOP吸附,Np(Ⅳ)、Np(Ⅵ)分别用HNO_3+HF、HNO_3+HF+Fe(NH_2SO_3)_2洗脱,从而达到定量分离。文中并对光的影响进行了讨论。最后简单叙述了用TIOP—萃淋树脂来分离Np(Ⅳ)、Np(Ⅴ)和Np(Ⅵ)的实验。     

溶剂萃取法分离测定高放废液中的α核素

研究了从高放废液泥浆离心母液中用HDEHP-TiOA、TiOA、TRPO分离237Np、239Pu、241Am等α核素的分离方法。提出了分离程序及总α的测定方法。分离流程对239Pu、237Np、241Am的回收率分别为99％、88％、99％。     

Method for fast separation of iodine isotopes on silver-containing membranes

A method for fast separation of iodine isotopes from the water coolant of a nuclear power facility, making possible maximal simplification of sample preparation, reducing it to filtering a sample acidified with ascorbic acid to pH = 3 through a silver-impregnated acetylcellulose membrane, has been developed for monitoring fuel-element seal tightness. Impurity ⁹⁹Mo, ¹⁸⁷W, ⁵¹Cr, and ²³⁹Np do not separate onto the membrane. The materials and reagents used are nontoxic, explosion-proof, and fire-proof. The time for analysis is reduced by a factor of 10. A point source makes it possible to increase the radiation detection efficiency, decrease the measurement time, and decrease the limit of detection by more than a factor of 10. __________ Translated from Atomnaya énergiya, Vol. 104, No. 4, pp. 238–241, April, 2008.     

腐殖酸对Np胶体行为的影响

在模拟高放废物深地质处置的低氧低浓条件下,探讨用膜过滤法研究Np胶体行为的可行性。实验研究结果表明:无腐殖酸存在时,在pH=1～13条件下,无机离子对237Np的测定无明显影响,237Np的液闪探测效率可达100%;增加闪烁液用量可消除腐殖酸对237Np的淬灭效应,过滤器对237Np的吸附可忽略不计,说明将过滤法应用于Np的胶体行为研究准确、可靠,操作简便。应用该方法对Np的不同价态和腐殖酸存在下的胶体行为进行了研究。Np(Ⅴ)无明显胶体行为,Np(Ⅳ)以真胶体形态存在,其浓度显著影响胶体行为;腐殖酸与Np(Ⅳ)能形成假胶体,从而提高了Np(Ⅳ)在溶液中的含量,有利于Np的迁移。腐殖酸是核素迁移研究必须考虑的重要影响因素。     

近红外光谱法直接测定后处理水相料液中硝酸浓度

硝酸浓度影响甚至决定铀钚元素在后处理料液中的分配比,所以在后处理工艺控制分析中,游离酸的测定占有重要地位,具有分析点多、分析频率高、时效性强等特点。现有的分析方法取样量大、分析速度慢,因此,建立新的游离酸快速分析方法,对于后处理工艺控制分析具有重要意义。在本工作中,应用自行研制的适合于我国后处理料液分析的近红外光纤光谱仪,结合PLS回归方法,建立了后处理水相料液游离酸的快速测量方法。该方法取样量小、操作简单、分析快速,适用于水相料液中硝酸含量的测定。所建立的铀酸数学模型对于料液中酸浓度的最低检测限为0.06mol/L;建立的钚酸数学模型对于含大量钚料液中酸浓度的最低检测限为0.12mol/L;相对误差小于10%,测量相对标准偏差s_r<5%。对后处理厂实际样品的分析表明,分析结果与草酸盐络合-定pH值滴定法结果一致,方法准确、可靠。     

The AMS measurement of 236U at CIRCE

Accelerator mass spectrometry(AMS) is an ultrasensitive technique for measuring long-lived actinides,e.g.,~(236)U,~(237)Np and Pu isotopes.In order to improve the detection limit for actinides abundance,and to increase the detection efficiency in actinides AMS measurement,a 16-strip silicon detector was used to identify actinides at the Center for Isotopic Research on Cultural and Environmental heritage in Caserta,Italy.The sensitivity of ~(236)U/~(238)U was 1×10~(-11) by special resolution and 5.0×10~(-12) by time resolution.The pulse height defect of~(236)U in an ion-implanted silicon detector in the low-energy range with 17.26 MeV is presented.     

Emission Probabilities of Gamma Rays from the Decay of 233Pa and 238Np,and the Thermal Neutron Capture Cross Section of 237Np

In order to determine the thermal neutron capture cross section of ²³⁷Np, the relevant γ emission probabilities of the 312-keV γ-ray from the decay of ²³³Pa and the 984-keV γ-ray from the decay of ²³⁸Np are deduced from the ratio of the emission rate to the activity. The emission rate and activity are measured with a Ge detector and a Si detector, respectively. The measured emission probability for 312-keV γ-ray is 41.6±0.9% and that for 984-keV γ-ray is 25.2±0.5%. The emission probabilities are used to correct the thermal neutron capture cross section of ²³⁷Np reported previously, and gives 168±6b. The neutron capture cross section is also determined as 169±6b by α-ray spectroscopic method. The measured emission probabilities and capture cross section are compared with others from references. By averaging these values deduced by different methods, the value of 169±4b is recommended as the thermal neutron capture cross section of ²³⁷Np for 2,200 m/s neutrons.     

N，N′-二甲基-N，N′-二辛基-3-氧杂-戊二酰胺对Np(Ⅳ，Ⅴ，Ⅵ)的萃取行为

²³⁷Np半衰期较长，具有较高的生物毒性，使其成为高放废液非α化过程中重点关注的核素之一。本工作采用新型的N,N′-二甲基-N,N′-二辛基-3-氧杂-戊二酰胺(DMDODGA)为萃取剂，研究了萃取剂浓度、水相初始硝酸浓度和温度等因素对DMDODGA萃取Np(Ⅳ)、Np(Ⅴ)、Np(Ⅵ)的影响。结果表明：随着DMDODGA浓度和水相初始硝酸浓度的增加，Np(Ⅳ)、Np(Ⅴ)、Np(Ⅵ)的分配比均增大。萃取剂浓度小于0.005 mol/L时，DMDODGA与Np(Ⅳ)生成1∶2型萃合物；萃取剂浓度大于0.005 mol/L时，DMDODGA与Np(Ⅳ)生成1∶3型萃合物。萃取剂浓度在0.1~1.0 mol/L范围内，DMDODGA与Np(Ⅴ)、Np(Ⅵ)均生成1∶2型萃合物。DMDODGA萃取Np(Ⅳ)、Np(Ⅴ)、Np(Ⅵ)的ΔH分别为-59.55、-22.02、-31.40 kJ/mol，3个反应均为放热反应，降低温度有利于反应的正向进行。     

Quantitative Analysis of Heavy Metals in Water Based on LIBS with an Automatic Device for Sample Preparation

Heavy metals in water can be deposited on graphite flakes,which can be used as an enrichment method for laser-induced breakdown spectroscopy(LIBS) and is studied in this paper.The graphite samples were prepared with an automatic device,which was composed of a loading and unloading module,a quantitatively adding solution module,a rapid heating and drying module and a precise rotating module.The experimental results showed that the sample preparation methods had no significant effect on sample distribution and the LIBS signal accumulated in 20 pulses was stable and repeatable.With an increasing amount of the sample solution on the graphite flake,the peak intensity at Cu Ⅰ 324.75 nm accorded with the exponential function with a correlation coefficient of 0.9963 and the background intensity remained unchanged.The limit of detection(LOD) was calculated through linear fitting of the peak intensity versus the concentration.The LOD decreased rapidly with an increasing amount of sample solution until the amount exceeded 20 mL and the correlation coefficient of exponential function fitting was 0.991.The LOD of Pb,Ni,Cd,Cr and Zn after evaporating different amounts of sample solution on the graphite flakes was measured and the variation tendency of their LOD with sample solution amounts was similar to the tendency for Cu.The experimental data and conclusions could provide a reference for automatic sample preparation and heavy metal in situ detection.     

Delayed gamma studies from photo-fission of Np for nuclear waste characterization

An active and non-destructive method is being established for detection of ²³⁷Np in nuclear waste barrels. The unique high energy decay gamma signature produced after photo-fission is analysed to deduce decay time parameters. A high purity ²³⁷Np sample was irradiated with bremsstrahlung photons and high energy gamma decay spectra were measured with BGO detectors for various irradiation durations. The analysis of decay spectra resulted in the formation of five decay groups, which can reproduce the experimental decay spectra within 10% accuracy. These parameters together with neutron decay groups are absolutely essential to quantify the nuclear material in waste barrels by photo-fission. The delayed decay gamma groups for ²³⁷Np nucleus are being reported for the first time.