Aktivierungsanalytische Untersuchung von Zirkoniumlegierungen

Durch Aktivierungsanalyse mit Reaktorneutronen (zerstörungsfrei und mit chemischer Aufarbeitung) sowie mittels zerstörungsfreier Untersuchungen an einem Neutronengenerator wurden O, Al, Si, P, Mn, Cu, Nb, Mo, Cd, Ti, Cr und Hf in Zirkoniumlegierungen bestimmt.     

Isotopenverdünnungsanalytische Multielementanalyse mit der Funkenquellen-Massenspektrographie

Es wird ein Verfahren zur Isotopenverdünnungsanalyse mit stabilen Isotopen unter Verwendung einer Funkenionenquelle und einem doppelfokussierenden Massenspektrographen beschrieben, welches die gleichzeitige Analyse mehrerer Elemente in pulverförmigen Feststoffen erlaubt.

Die Leistungsfähigkeit des Analysenverfahrens wild am Beispiel der Spurenanalyse geologischer Standardproben demonstriert.

Das Analysenverfahren erlaubt die Bestimmung von Spurenkonzentrationen bis in den ppb-Bereich mit Standardabweichungen zwischen 2 und 10%.     

强流脉冲电子束作用下金属锆的微观结构与应力状态

利用强流脉冲电子束 (HCPEB) 技术对金属纯锆进行表面处理, 采用X射线衍射, 扫描电子显微镜及透射电子显微镜详细分析了辐照诱发的表层微观结构和缺陷. X射线分析结果表明, HCPEB辐照后在材料表层诱发幅值为GPa量级的压应力, 并形成{0002}, {1012}, {1120}及{1013}织构. 表层微观结构观察表明, 与其他金属材料不同, HCPEB辐照在材料表层诱发的熔坑数量极少, 多次轰击甚至几乎没有表面熔坑的形成. 此外, 在快速的加热和冷却状态下, 在表面熔化层形成大量的超细晶粒结构, 同时诱发马氏体相变和强烈的塑性变形. 1次HCPEB辐照后表层内形成的变形微结构以位错为主, 孪晶数量较少; 5 次辐照样品的位错密度迅速增高, 孪晶数量也显著增加; 10次辐照后样品中的变形微结构以变形孪晶为主, 且出现二次孪晶现象. 表层晶粒内部变形的晶体学特征不仅决定了表层的织构演化行为, 而且还起到细化晶粒的作用, 为纯锆及锆合金表面强化提供了一条有效的途径. 关键词： 强流脉冲电子束 纯锆 微观结构 应力状态     

Zur Bestimmung der radiolytischen Zersetzung von Tributylphosphat (TBP) unter Verwendung von 95Zr und 95Nb

Unter Verwendung der hochauflösenden γ-Spektrometrie wurde das Verhalten von ⁹⁵Zr und ⁹⁵Nb in Extraitionsprozessen untersucht. Die Versuche wurden mit Tributylphosphalproben, die wir im Gleichgewicht mit wäβrigen Salpetersäurelosungen bestrahlten, durchgefuhrt. Für ⁹⁵Nb wurde ein unregelmäβiges Verhalten während der Extraktionsprozesse festgestellt. Aus diesem Grunde ist zur Abschätzung der radiolytischen Zersetzung von TBP die summarische Messung der ⁹⁵Zr- und ⁹⁹Nb-γ-Strahlungsintensität nicht ausreichend.     

Disordered bcc γ-phase to δ-phase transformation in Zr-rich U-Zr alloy

The transformation mechanism of hexagonal delta phase from the disordered bcc gamma phase has not been reported before in the Zr-rich U–Zr alloy system. With the help of X-ray diffraction, transmission electron microscopy (TEM) and high-resolution TEM analyses it was shown that the gamma to delta conversion takes place by the lattice collapse mechanism of omega transformation. It was also ascertained that a higher aging temperature or time promotes the growth of all four variants of the delta phase within a parent gamma grain. In addition, ab initio electronic structure calculations showed that the bcc to hexagonal transformation, involving partial ordering of the parent bcc phase followed by (111) plane collapse, is energetically favorable.     

Effect of Sn and Nb on generalized stacking fault energy surfaces in zirconium and gamma hydride habit planes

We have investigated the effects of Sn and Nb on dislocation properties in a Zr lattice to elucidate the role of these alloying elements in hydride nucleation processes. According to experimental observations, γ-hydride habit planes are close to the prismatic plane in pure Zr and close to the basal plane in Zircaloy. Dislocation loops are observed around hydride precipitates, implying they play a part in hydride formation. Our ab initio generalized stacking-fault energy calculations showed remarkable effects of Sn on unstable-stacking energy and stacking-fault energy: these parameters for basal slip were considerably reduced while those for prismatic slip were increased in the presence of Sn. These results suggest selective stabilization and enhancement of dislocation spreading in the basal plane, promoting possible elementary processes of hydride precipitation with basal habit plane, i.e. screw-dislocation spreading and edge-dislocation emission in the basal plane.     

Anodic oxide growth on Zr in neutral aqueous solution

Anodization and subsequent cathodic reactions on a thin-film sample of Zr were studied with in-situ neutron reflectometry (NR) and electrochemical impedance spectroscopy (EIS). The NR results during anodization showed the originally 485 Å thick Zr film generally behaved similar to a bulk electrode in neutral solution. The anodization ratio measured at applied potentials increased in steps of 0.5 V was somewhat higher than the value determined by coulometry, while the Pilling Bedworth ratio is in good agreement with published data. Thickening of the oxide layer, accelerated immediately after each potential increase, gradually decreased over several hours, but remained nonzero even after ～12 h. The thickened oxide eventually cracked when its thickness reached ～120 Å, causing loss of passivation. Surprisingly, neither the anodization ratio nor the Pilling Bedworth ratio showed any discontinuity at the time of oxide cracking, and the EIS behaviour remained qualitatively as before. This observation is taken as the evidence that the cracked and intact regions of the electrode behave more or less independently as parallel electrodes. When the potential was eventually switched to cathodic polarity, NR shows, as expected, that the effects of oxide cracking were irreversible. However, the electrode resistance recovered partially suggesting the cracks were rapidly plugged with newly formed oxide.     

Solvent-Free Synthesis of Nano Zirconium Phenylphosphonates with Molten Phenylphosphonic Acid

Nanosized α-zirconium phenylphosphonate particles were successfully prepared by the reaction between different zirconium sources and molten phenylphosphonic acid in the absence of solvent. The resultant nanoplates exhibit particle sizes in the range of 15 to 30 nm. The use of a topotactic anion exchange method starting from α-zirconium phosphate instead resulted in the generation of 15 to 180 nm plates, while also resulting in nanoparticles with a higher degree of crystallinity. The topotactic anion exchange of the phosphate groups by phenylphosphonate groups could be performed to completion when performed in molten phenylphosphonic acid. Characterization of both the final products as well as the individual steps in the anion exchange were performed by powder XRD, fast neutron activation analysis, TGA, FTIR spectroscopy, TEM, solid-state NMR and XPS.     

Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach

Solid-state NMR experiments on ²H, ³¹P, ¹³C, and ¹H nuclei, including ³¹P T₁, ¹H T₁, and ¹H T_1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D₂O and/or CD₃OD. The ¹³C{¹H} CP MAS NMR experiment performed for compound 1-CD ₃ OD (Zr (HPO₄)₂ ^. 0.2CD₃OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature ²H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD₃ rotations around the C₃-axis. It has been demonstrated that the intercalated species, D₂O and CD₃OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Thus, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.     

Polar Isotactic and Syndiotactic Polypropylenes by Organozirconium-Catalyzed Masking-Reagent-Free Propylene and Amino–Olefin Copolymerization

Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking-reagent-free propylene and amino–olefin (AO, CH₂=CH(CH₂)_xNⁿPr₂, x=2, 3, 6) copolymerizations using the activated precatalysts rac-[Me₂Si(indenyl)₂]ZrMe₂ and [Me₂C(Cp)(fluorenyl)]ZrMe₂, respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino-olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.