Initiation process of L‐lactide polymerization carried out with zirconium(IV) acetylacetonate

Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)₄] as an initiator was investigated. In the reaction between Zr(acac)₄ and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004     

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     

Beiträge zur Mikrobestimmung von Kohlenstoff-14 und Tritium

Die Verwendung Con¹⁴C und Tritium zur Lösung kinetischer und analylischer Probleme erfordert zuverlässige Analysenmethoden. Es wird iiber die Herstellimg von Meβgasen durch Naβcerbrennung mil Chromsäure-Jodsäure-Gemischen, Trockenverbrennung in Gegenwart Con Katalysatoren wie Kupferoxid, Kobaltoxid und Zersetzungsprodukte des Silberpermanganats und durch Umsetziingentm geschlossenen Rohr berichtet. Die Aktivitätsniessungen erfolgten auf cerschiedene IVeise. Hier werden besonders die Ergebnisse diskutiert, die durch Ionisationskammermessungen erzielt wurden. Schlieβlich werden einfache Apparaturen zur routinemäβigen Durchfiihrung von Mikroanalysen beschrieben.     

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%.     

Mossbauer investigations of corrosion environment influence on Fe valence states in oxide films of zirconium alloys

Mössbauer investigations about iron atom redistribution in oxide films of zirconium alloys subjected to corrosion at 500°C in pure oxygen and water pair have been analysed. The alloys were also subjected to autoclave conditions at a pressure of 10.0 MPa and autoclave conditions at 350°C and at a pressure of 16.8 MPa, using distilled water and water with additives of lithium and fluorine. It is shown that, depending on the corrosion environment, various compounds of iron, such as α-Fe₂O₃, Fe₃O₄, and FeO, as solid solutions of iron in ZrO₂ are formed in oxide films.     

金属卟啉配合物在无机层状框架中的插入组装及光学性能

利用插入化学法,将金属卟啉配合物——四苯基卟啉合银(Ⅱ),组装到改性磷酸锆(十二烷基三甲基铵磷酸锆)无机层状物中.配合物与改性磷酸锆作用后,层状框架的层间距由3.00nm调整到1.96 nm,卟啉的Soret吸收带和发射光谱都出现明显的位移,其中最大吸收由421 nm红移到429 nm,最大发射由651 nm红移到65...     

纯锆上离子注入钇和镧后的表面分析

用金属蒸汽真空弧源，以40kV加速电压对纯锆样品分别进行了10¹⁶—10¹⁷/cm²的钇、镧离子注入，注入温度约为130℃.然后对注入样品进行表面分析.x射线光电子能谱分析表明，注入的钇以Y₂O₃形式存在，镧以La₂O₃形式存在.俄歇电子能谱表明，纯锆基体表面的氧化膜厚度随着离子注入剂量的增加而增加，当离子注入剂量达到10¹⁷/cm²时，氧化膜的厚度达到了最大值.卢瑟福背散射显示镧层的厚度约为30nm，同时直接观察到当离子注入剂量为(La+Y)10¹⁷/cm²时，纯锆样品表面发生了严重的溅射. 关键词： 纯锆 钇和镧离子共注入 卢瑟福背散射 x射线光电子能谱     

Effect of Hydrolysis Conditions on the Direct Formation of Nanoparticles of Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

The effect of the cation concentration, hydrolysis temperature, and composition in the CeO₂–ZrO₂ system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO₂ were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm³ by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm³ at the starting composition of 50 mol% ZrO₂ under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH₄)₂Ce(NO₃)₆. Ceria–zirconia solid solutions containing large amount of ZrO₂ maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h.     

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.     

Fabrication and Optimization of Poly(vinyl alcohol)/Zirconium Acetate Electrospun Nanofibers Using Taguchi Experimental Design

This paper presents an investigation regarding poly(vinyl alcohol)/zirconium acetate (organic–inorganic) (PVA/Zrace) nanofibers prepared by electrospinning which could be used as a precursor for fabricating ceramic metal oxide nanofibers. The effect of some processing variables, including polymer solution concentration, tip to collector distance and applied voltage of electrospinning, and the amount of Zrace and their interactions, on the diameter of the nanofibers were studied. Taguchi experimental design and a statistical analysis (ANOVA) were employed and the relationship between experimental conditions and yield levels determined. It was concluded that to obtain a narrow diameter distribution as well as maximum fiber fineness, a polymer concentration of 10 wt%, tip to collector distance of 18 cm and applied voltage of 20 kV variables were the optimum. Furthermore, it was also concluded that the ratio of Zrace (6 g) to PVA solution (10% wt) played an important role for achieving the minimum fiber diameter. Under these optimum conditions, the diameters of the electrospun composite fibers ranged from 86 nm to 381 nm with a diameter average of 193 nm. The experiments were done with Qualitek-4 software with “smaller is better” as the quality characteristics. The optimized conditions showed an improvement in the fibers diameter distribution and the average fibers diameter showed good resemblance with the result predicted using the Taguchi method and the Qualitek-4 software. The ANOVA results showed that all factors had significant effects on the fibers diameter and distribution, but the effect of PVA concentration and zirconium acetate were more significant than the other factors.