阳离子光引发剂[Cp-Fe-diphenylether]+PF6-的合成和光引发性能的研究

制备了一种具有芳茂铁盐结构的新型阳离子光引发剂[环戊二烯基-铁-二苯醚]六氟磷酸盐([Cp-Fe-diphenylether]^ PF6^-),并研究了其作为阳离子光引发剂在高压汞灯下引发环氧预聚体的光引发活性。发现其由d-d跃迁产生的394nm和462nm的吸收峰同I-261([环戊二烯基-铁-异丙苯]六氟磷酸盐)相比红移约10nm,且摩尔吸光系数ε有所提高;以高压汞灯为辐射光源,对脂环族环氧ERL4221和TDE85及脂肪族环氧树脂E44均有良好的光引发活性;与增感剂过氧化苯甲酰(BPO)混合使用,其光引发活性高于碘鎓盐SR-1012;光照后仍具有较强的聚合活性。     

离子液体用于溶剂萃取铀酰离子的初步研究

初步研究了以咪唑类离子液体1-辛基-3-甲基咪唑六氟磷酸盐([C8mim][PF6])、1-丁基-3-甲基咪唑六氟磷酸盐([C4mim][PF6])和季胺类离子液体三辛基甲基氯化铵([N8881][Cl])为稀释剂,TBP为萃取剂,从硝酸介质中萃取铀酰离子。研究结果表明,铀的萃取分配比随水相初始硝酸浓度的增加而增加,季胺类离子液体略好于咪唑类离子液体,但都比对照稀释剂异辛烷差。研究了以碳酸胍为反萃剂的反萃条件。碳酸胍在实验条件下均能从这3种离子液体萃取体系中定量反萃铀酰离子,解决了用离子液体萃取铀酰离子中的反萃及离子液体的循环使用问题。     

二醋酸纤维素薄膜剂量计的制备和性能研究

为了改善醋酸纤维素薄膜剂量计在γ辐射剂量测定中稳定性欠佳的问题,拓展其辐射测量应用范围,采用离子液体均相乙酰化纤维素方法制得的二醋酸纤维素(CDA)粉末为原料,优化CDA薄膜制备工艺,研究其γ辐射变色性能及稳定性,制备适用于γ辐射剂量测量且性能优良的CDA薄膜剂量计。基于CDA的辐射变色机理,该薄膜剂量计在270 nm的单位厚度吸光度与吸收剂量存在良好的线性关系,剂量率、CDA的取代度和辐照气氛对薄膜的工作曲线影响较小。CDA薄膜剂量计的剂量检测量程为50～400 kGy,扩展不确定度为8.8%(K=2),辐照后24 h内吸光度测试稳定,具有良好的辐照稳定性,基本满足工业上对于辐射剂量计的使用要求,有望应用于γ辐射剂量的测量。     

羰基锝硝基咪唑化合物99Tcm (CO)3-MNLS的标记和生物学评价

本文采用直接标记法在水相中将羰基锝中间体[99Tcm (CO)3( H2O)3]+与含磷酸基团的硝基咪唑衍生物2-(2-甲基-5-硝基咪唑-1-基)乙基磷酸盐(2-( 2-methyl-5-nitro-1 H-imidazol-1-yl)ethyl dihydrogen phosphate,MNLS)配位得到99Tcm...     

铀(Ⅵ)在氯化1-丁基-3-甲基咪唑中的电化学性质

通过循环伏安和计时电位等电化学测量方法研究了硝酸铀酰在亲水性离子液体--氯化1-丁基-3-甲基咪唑([BMIM]C1)中的电化学过程.结果表明,UO2+2在离子液体[BMIM]Cl中转移2个电子,一步还原为UO2.当扫描速率为10～100 mV/s、体系温度为353 K、UO2+2浓度为13.27 mmol/L时,电极...     

γ辐照对N,N,N′,N′-四丁基-3-氧-戊二酰胺萃取性能的影响

N,N,N′,N′-四丁基-3-氧-戊二酰胺(TBOPDA)对锕系和镧系元素具有较好的萃取性能和较高的辐照稳定性。本文主要研究了辐照对纯TBOPDA和稀释后的TBOPDA萃取性能的影响。研究结果表明,该萃取剂具有较强的辐照稳定性。纯萃取剂在辐照剂量达到1000kGy时,对铀的萃取分配比才有明显下降;;达到100kGy时对铕的萃取分配比有明显下降。稀释剂的加入会使萃取剂辐照稳定性有所下降。     

二醋酸纤维素薄膜剂量计的制备和性能研究

为了改善醋酸纤维素薄膜剂量计在γ辐射剂量测定中稳定性欠佳的问题,拓展其辐射测量应用范围,采用离子液体均相乙酰化纤维素方法制得的二醋酸纤维素（CDA）粉末为原料,优化CDA薄膜制备工艺,研究其γ辐射变色性能及稳定性,制备适用于γ辐射剂量测量且性能优良的CDA薄膜剂量计。基于CDA的辐射变色机理,该薄膜剂量计在270 nm的单位厚度吸光度与吸收剂量存在良好的线性关系,剂量率、CDA的取代度和辐照气氛对薄膜的工作曲线影响较小。CDA薄膜剂量计的剂量检测量程为50~400 kGy,扩展不确定度为8.8%（K=2）,辐照后24 h内吸光度测试稳定,具有良好的辐照稳定性,基本满足工业上对于辐射剂量计的使用要求,有望应用于γ辐射剂量的测量。     

γ辐照对N，N，N’，N’-四丁基-3-氧-戊二酰胺萃取性能的影响

N，N，N’，N’-四丁基-3-氧-戊二酰胺(TBOPDA)对锕系和镧系元素具有较好的萃取性能和较高的辐照稳定性。本文主要研究了辐照对纯TBOPDA和稀释后的TBOPDA萃取性能的影响。研究结果表明，该萃取剂具有较强的辐照稳定性。纯萃取剂在辐照剂量达到1000kGy时，对铀的萃取分配比才有明显下降；达到100kGy时对铕的萃取分配比有明显下降。稀释剂的加入会使萃取剂辐照稳定性有所下降。     

甲异羟肟酸γ辐照稳定性

甲异羟肟酸(FHA)是有望用于乏燃料后处理的新型无盐络合剂。本工作用紫外分光光度法研究了FHA的γ辐照稳定性,并且研究了硝酸和甲基肼对FHA辐照稳定性的影响。结果表明,当剂量为10~1000 kGy时,FHA在水溶液中的辐照稳定性随FHA浓度的增加而增大,但随剂量的增加而降低;在HNO3-0.2 mol/L FHA体系中,当HNO3浓度为0.2 mol/L时,FHA的辐照稳定性略有增加,但当c(HNO3)≥0.5 mol/L时,FHA的辐照稳定性降低;在甲基肼-1.0 mol/L HNO3-0.2 mol/L FHA体系中,FHA的辐照稳定性随甲基肼浓度的增加而增大。     

核燃料循环中所用含磷萃取剂的辐照稳定性研究

对核燃料后处理以及高放废液处理中所用的含磷萃取剂的辐照稳定性已经进行了广泛的研究。对正辛基苯基-N，N’-二异丁基胺甲酰甲基氧化膦(CMPO)、二(2-乙基己基)磷酸(DEHPA)以及混合三烷基氧化膦(TRPO)等的辐照稳定性的研究进行了综述。主要介绍了CMPO、DEHPA和TRPO的辐解产物；辐照对萃取和保留的影响以及辐照后溶剂的净化方法。     

Laser photolysis of ionic liquid [bmim][PF6]

Photoinduced chemical reactions of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF_6]) were studied by laser photolysis at a wavelength of 266 nm.Excited triplet state ~3[bmim]~ was observed,radical cation [bmim]~(2 ) and neutral [bmim] radical via photoionization were also formed.Energy transfer from ~3[bmim]~ toβ-carotene was confirmed.Oxidation via one electron transfer from TMPD to ~3[bmim]~ was also observed and the rate constant was determined to be 1.2×10.5 L.mol~(-1).s~(-1).The reaction of [bmim][PF_6] with hydrated electron (e_(aq)) was confirmed by laser photolysis in aqueous solution.     

Effects of gamma-ray irradiation on crevice corrosion repassivation potential of stainless steel in high temperature diluted simulated seawater

The crevice corrosion repassivation potentials (E_R,CREV) of type 304 stainless steel (304 SS) were measured in high temperature (373–553 K), diluted simulated seawater under gamma-ray irradiation, in order to confirm the effects of gamma-ray irradiation on the crevice corrosion behavior of a representative stainless steel in seawater. Overall, for high temperatures, the E_R,CREV values decreased with increasing chloride ion concentration, which was the same as the behavior observed under the non-irradiated condition. The E_R,CREV values measured under gamma-ray irradiation were the same or slightly higher than E_R,CREV values measured under the non-irradiated condition when the [Cl^?] was the same. Consequently, it was confirmed that the threshold potential of crevice corrosion of 304 SS for the gamma-ray irradiation of 1.8 kGy at least did not deteriorate compared with the non-irradiated condition. Under the conditions of this work (seawater composition, [Cl^?] range, dose rate, absorbed dose, flow rate, etc.), the crevice corrosion of 304 SS could be suppressed by maintaining the potential below the threshold potential which was determined approximately as ?0.3 V vs. SHE even for the irradiated condition at temperatures up to 553 K.     

InGaAsP多量子阱激光二极管及其组件的γ辐射效应

本工作进行多量子阱激光二极管及其组件的γ辐照实验研究,总剂量（以Si计）达5.5×10⁴Gy。结果表明：多量子阱激光二极管抗γ射线辐照能力很强,在实验总剂量下,裸管形式的多量子阱激光二极管的P-I特性、I-V特性及中心波长基本未变化。而多量子阱激光二极管组件因包含光学窗口、耦合透镜及光纤等附属光学元件,这些附属元件受γ辐照后光学性能下降,最终导致激光二极管组件输出光功率随总剂量增大而下降,停止辐照后,不需加偏置,在室温下即能发生退火,使得斜率效率逐渐回升。     

Effects of seawater components on radiolysis of water at elevated temperature and subsequent integrity of fuel materials

Effects of seawater components on radiolysis of water at elevated temperature have been studied with a radiolysis model and a corrosion test under gamma-ray irradiation conditions to evaluate the subsequent influence on integrity of fuel materials used in an advanced boiling water reactor. In 2011, seawater flowed into the nuclear power plant system of the Hamaoka Nuclear Power Station Reactor No. 5 during the plant shutdown operation. The reactor water temperature was 250 °C and its maximum Cl^? concentration was ca. 450 ppm when seawater was mixed with reactor water. The radiolysis model predicted that the main radiolytic species were hydrogen, oxygen and hydrogen peroxide. Concentrations of radiolytic products originating from Cl^? and other seawater components were found to be rather low. The dominant product among them was ClO₃^? and its concentration was found to be below 0.01 ppm for a 10⁵ s irradiation period. No significant corrosion of zircaloy-2 and 316L stainless steel was found in the corrosion test. These results led to the conclusion that the harmful influence of radiolytic products originating from seawater components on integrity of fuel materials must be smaller than that of Cl^? which is the main ionic species in seawater.     

Formation of platinum nanoparticle colloidal solution by gamma-ray irradiation

Platinum nanoparticle colloidal solution with a small amount of impurities was formed from a suspension of hexahydroxy platinic acid (SHHPA) by gamma-ray irradiation to suppress changes in water chemistry such as electrical conductivity and concentration of impurities in the reactor water during noble metal chemical addition in plant operation. The SHHPA was prepared from sodium hexahydroxyplatinate solution by using an H-type cation exchange resin. Optimum conditions for formation of the platinum nanoparticle colloidal solution were the following: absorbed dose of gamma-ray irradiation, >6 kGy; pH of solution, >8.2; air saturation; no methanol addition. Characteristics of the formed platinum nanoparticles were as follows: mean particle size, 2.3 ± 0.5 nm; particle charge, negative; isoelectric point at a pH of 3.5 ± 0.1; the chemical compound consisted mainly of platinum dioxide without platinum metal. No precipitation of platinum nanoparticles was observed after storage time of 1 year without any stirring in a room where the temperature varied from about 10 to about 35 °C.     

Effect of gamma radiolysis on pit initiation of zircaloy-2 in water containing sea salt

In spent fuel pools at the Fukushima Daiichi Nuclear Power Station (1F), seawater was injected for cooling purposes after the tsunami disaster in March 2011. It is well known that the chloride in the seawater has the potential to cause localized corrosion (e.g., pitting corrosion) in metals. In this study, we evaluated the pitting potentials of zircaloy-2, the material used in the fuel cladding tubes in 1F, as a function of chloride concentration. To accomplish this, we used artificial seawater under gamma-ray irradiation and investigated the effect of radiolysis on pit initiation of zircaloy-2 in water containing sea salt. Changes in the composition of water containing sea salt were analyzed as well, both before and after gamma-ray irradiation. The characteristics of the resultant oxide films formed on zircaloy-2 were evaluated by X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The experimental results showed that the pitting potential under irradiation was slightly higher than that under conditions in which no radiation was present, and that the pitting potential decreased with increasing chloride concentration in the presence as well as the absence of radiation. Solution analyses for water containing sea salt showed that hydrogen peroxide was generated by irradiation. The oxide film was composed of zirconium oxide and was made thicker during the irradiation. The higher pitting potential could thus be explained by the capacity of hydrogen peroxide to oxidize the surface and enhance oxide film formation. Under gamma-ray irradiation, the zircaloy-2 surface with an oxide film formed by radiolysis products was found to be resistant to pitting in the presence of chloride.     

氟树脂F2313辐射降解产物研究

应用气相色谱法、质谱法及离子选择电极分析法研究了氟树脂F2313在真空、空气和氮中经γ射线辐照后发生的降解反应。实验测定了HF，HCl和CO2的产额（G）值。研究结果发现，生成的HF，HCl的随剂增大而增大。当剂量为50kGy时，仅在空气气氛中检测到有CO2产生，CO2的质量随剂量的增大而增大。当剂量达到250kGy时，在真空、氮气、空气三种气氛中都有H2产生，H2的随剂量的增大而增大，空气气氛中产生的H2的质量最少。辐照后的样品经红外光谱（IR）分析发现有-CF-CF－基因。     

氮杂多环芳烃/离子液体萃取体系的伽马辐射效应

乏燃料后处理分离体系的辐射稳定性是其实际应用前需解决的重要问题。采用傅里叶变换红外光谱(FTIR)、超高效液相色谱/四级杆飞行时间质谱联用(UPLC/Q-TOF-MS)等方法系统研究了IB-BTP/[C₂mim][NTf₂]、CA-BTP/[C₂mim][NTf₂]和CA-BTPhen/[C₂mim][NTf₂]三种典型的氮杂多环芳烃/离子液体萃取分离体系的γ辐射效应,并通过Eu³⁺萃取实验对辐照前后体系的萃取性能变化进行了对比。结果表明:三种萃取剂在[C₂mim][NTf₂]离子液体中的辐射稳定性顺序为:CA-BTP>IB-BTP≈CA-BTPhen;三种体系的辐解产物主要为[C₂mim][NTf₂]离子液体辐解产生的·CF₃、·[C₂mim]⁺、·H等自由基进攻氮杂多环芳烃...     

Radiation synthesis and characterization of polyacrylic acid hydrogels

The pH-sensitive polyacrylic acid （PAA） hydrogels were synthesized by gamma-ray irradiation at an ambient temperature. The influences of dose, monomer concentration, cross-linking agent content, pH, and ionic strength on the swelling ratio （SR） of the PAA hydrogels were investigated in detail. The results show that the SR of the hydrogel decreases with an increase in the dose, monomer concentration, and cross-linking agent content. In alkaline solution, the SR of the hydrogels is much higher than that in acid solution. Also, the ionic strength can influence the SR of the hydrogels. The more the concentration, the lower the SR.