Transformation mechanisms between solid material and ion in solutions by radiolysis and sonolysis

放射性和sonolytic redox反应的技术，它是一种在被调查的核材料中形成的长寿命燃料产品。一种氧化条件下最稳定的化学品种类（Tc（VII）O_4）是由电子线性加速器产生的低氧化剂辐照的化学品，以及纳米粒子（IV）氧化物水合物的形成（Tc（IV）O_2·nH_2O ）被确认。这种反应是由Tc（VII）和水分子放射性产生的氢化电子的双分子反应触发的。降低过程的机理使Tc（VI）和Tc（V）分离反应在20℃以下或他大气层下的玻璃电池中的平板底（Tc（VII）O_4）解决方案和Tc（IV）O_2-nH_2O胶体解决方案（[Tc] = 0.1 mM）被放大（200 kHz， 200 W）。在本研究中没有减少TcO_4的数量。However，它被观察到，在一个明确的解决方案中，TcO_2·nH_2O胶体被分解在大气层下30分钟内完全分解的超声波处理，TcO_4最终生产。TcO_4的生产在t-butyl醇（OH基分子的有效清除剂）的存在中被抑制，表示Tc（IV）被OH基分子氧化化（由水分子分离产生），在超声波中产生的热空化气泡。TcO_4以下的形成率。他的大气层比大气层下的大气层要慢。这可以归因于碰撞泡沫中有效的最大温度的差异。因为他的热传导性比Ar高得多，所以热传导有效地从泡沫到环绕液体。所以，用氩填充的温度，他应该比用氩填充的温度更低，以较低的OH形成率结果。

Radiolytic and sonolytic redox reactions of technetium that was one of long-lived fission products formed in the nuclear materials were investigated. An aqueous solution of pertechnetate (Tc(VII)O_4) that was the most stable chemical species under oxidative conditions was irradiated with bremsstrahlung produced by an electron linear accelerator, and the formation of nanoparticles of technetium(IV) oxide hydrate (Tc(IV)O_2・nH_2O ) was confirmed. This reaction was triggered by a bimolecular reaction of Tc(VII)and hydrated electrons produced by radiolysis of water molecules. The mechanisms of the reducing processes involving disproportionation reactions of Tc(VI) and Tc(V) were clarified.Aqueous pertechnetate (Tc(VII)O_4) solutions and Tc(IV)O_2-nH_2O colloids solutions ([Tc] = 0.1 mM)were sonicated (200 kHz, 200 W) in a glass cell with flat bottom under Ar or He atmosphere at 20℃. No reduction of TcO_4 was observed in this study. However, it was observed that TcO_2・nH_2O colloids dispersed in an aqueous solution were completely dissolved by ultrasonic treatment within 30 min under Ar atmosphere, and TcO_4 was eventually produced. The production of TcO_4 was considerably suppressed in the presence of t-butyl alcohol (an effective scavenger of OH radicals), indicating that Tc(IV) was oxidized by OH radicals (produced by dissociation of water molecules) in hot cavitation bubbles created by ultrasound. The formation rate of TcO_4 under. He atmosphere was slower than that under Ar atmosphere. This can be attributed to a difference of the effective maximum temperature in the collapsing bubbles. Because thermal conductivity of He is much higher than Ar, thermal transport effectively occurs from the bubbles to the surrounding liquid. Thus, temperature of cavitation bubbles filled with He should be lower than those filled with Ar, resulting in the slower OH formation rate.