微调镝(Ⅲ)离子配位环境提升单离子磁体有效能垒

对于合成化学家来说,通过合成策略调控单离子磁体的磁动力学是一项艰巨的任务。我们以三（2-羟基亚苄基）三氨基胍配体（L）合成了2例单核Dy（Ⅲ）配合物[Dy（L）₂（H₂O）₂]ClO₄·2H₂O·2CH₃CN·CH₃OH（1）和[Dy（L）₂（H₂O）₂]CF₃SO₃·4H₂O·2CH₃OH（2）。对其结构和磁性研究表明,不同的抗衡阴离子对于配合物1和2的动态磁行为有显著影响。2个配合物中,Dy（Ⅲ）中心都具有三角形十二面体D_2d对称性,在零直流场下表现出单离子磁体的行为,其有效能垒分别为358 K（1）和309 K（2）。结构参数对比表明轴向位置的键长和键角微小变化对轴向配体场产生了显著的影响,而轴向配体场的微小变化导致了2个配合物交流磁性的差异。     

Recent Developments in Lanthanide Single‐Molecule Magnets

Single‐molecule magnets (SMMs) exhibiting slow relaxation of magnetization of purely molecular origin are highly attractive owing to their potential applications in spintronic devices, high‐density information storage, and quantum computing. In particular, lanthanide SMMs have been playing a major role in the advancement of this field because of the large intrinsic magnetic anisotropy of lanthanide metal ions. Herein, some recent breakthroughs that are changing the perspective of the field are highlighted, with special emphasis on synthetic strategies towards the design of high‐performance SMMs.     

Effects of substituents on bridging ligands on the single‐molecule magnet properties of Zn2Dy2 cluster complexes

Two new Zn₂Dy₂ complexes were constructed from Zn (II) salen‐type Schiff base complex fragment and 2,6‐pyridinedimethanol (H₂pdm) or its Br‐substituted analogue (4‐bromopyridine‐2,6‐diyl)dimethanol (H₂Brpdm); their molecular formulas are [Zn₂Dy₂(L)₂(pdm)₂(MeOH)₂](ClO₄)₂ [ 1 , H₂L = N, N′‐ bis(3‐methoxysalicylidene)‐1,3‐diaminopropane] and [Zn₂Dy₂(L)₂(Brpdm)₂(MeOH)₂](ClO₄)₂ [ 2 ], the Dy (III) ions of which have a NO₇ triangular dodecahedral coordination sphere. The two complexes show not only ferromagnetic interaction but also field‐induced single‐molecule magnet (SMM) behavior, which are rare Dy (III)‐containing cluster complexes with the NO₇ triangular dodecahedral coordination sphere that can show good magnetic relaxation. The energy barrier value of complex 2 is higher than those of complex 1 and the Dy (III) complexes with the DyNO₇ triangular dodecahedral coordination configuration reported in the literature.     

纳米锌镀层在硫酸中的腐蚀和缓蚀机理

用失晕法测试了纳米锌镀层和0^#锌片在0．2mol／L硫酸介质中的腐蚀性能．结果表明纳米锌镀层的耐腐蚀性要远优于锌片，且在一定的实验条件下，纳米锌镀层的腐蚀速率为一常数．另外，本文还研究了溴化十六烷基吡啶和吡啶及其甲基衍生物在硫酸介质中对纳米锌镀层和0^#锌片的缓蚀性能．其中溴化十六烷基吡啶和3-甲基吡啶的缓蚀性能较好．并用密度泛函B3LYP方法和Onsager溶剂化模型，在6-31G水平上优化了溴化十六烷基毗啶、3-甲基吡啶和4-甲基毗啶分子的几何构型，用其电子结构数据探讨了它们的缓蚀机理。     

纳米ZnO胶体可见发射机制的研究

关于ZnO可见发射机制的讨论目前尚无定论。本文研究了不同颗粒尺寸的纳米晶ZnO胶体的发射性质,观测到两个发射带,其中之一是激子发射,另一个是可见发射;发现两个发射带的峰值能量之间存在线性关系,并由此提出了可见发射机制是来自导带的电子到深陷阱的跃迁。     

MEASUREMENT OF NON-UNIFORM RESIDUAL STRESSES BY COMBINED MOIRE INTERFEROMETRY AND HOLE-DRILLING METHOD： THEORY, EXPERIMENTAL METHOD AND APPLICATIONS

Hole-drilling method is one of the most convenient methods for engineering residual stress measurement. Combined with moiré interferometry to obtain the relaxed whole-field displacement data, hole-drilling technique can be used to solve non-uniform residual stress problems, both in-depth and in-plane. In this paper, the theory of moiré interferometry and incremental hole-drilling (MIIHD) for non-uniform residual stress measurement is introduced. Three dimensional finite element model is constructed by ABAQUS to obtain the coefficients for the residual stress calculation. An experimental system including real-time measurement, automatic data processing and residual stresses calculation is established. Two applications for non-uniform in-depth residual stress of surface nanocrystalline material and non-uniform in-plane residual stress of friction stir welding are presented. Experimental results show that MIIHD is effective for both non-uniform in-depth and in-plane residual stress measurements. The project supported by the FRAMATOME ANP     

光电变色器件用纳米晶氧化钛薄膜的微结构与特性

纳米晶TiO2薄膜在光电变色器件中具有很重要的作用。它的微结构直接影响染料的吸附、光的散射以及电荷输运的特性。因此，探索TiO2薄膜的微结构(如粒径、表面形貌和厚度等)及光电性能是非常有意义的。采用电子束蒸发工艺制备了光电变色器件用纳晶TiO2薄膜，利用原子力显微镜、X射线衍射、俄歇电子能谱等手段对纳米晶TiO2薄膜的表面形貌、结晶状态及组分进行了分析。从理论上研究和讨论了纳米晶TiO2薄膜晶粒尺寸对光电性能的影响，并用量子限制效应解释了吸收光谱峰值波长随粒径减小而发生蓝移的现象。     

纳米复合永磁Pr9Fe74Co12B5Snx(x=0, 0.5)的磁化行为与磁黏滞性

用熔体快淬法制备了纳米复合永磁样品Pr₉Fe₇₄Co₁₂B₅ 与Pr₉Fe₇₄Co₁₂B₅Sn_0.5，分析了样品的起始磁化、反磁化过程，测得样品的总磁化率、可逆磁化率以及样品的磁黏滞性.结果表明，两样品在室温下均表现为单一硬磁相磁化行为，在低温下表现为双相行为，且由于添加Sn后使晶粒均匀化从而导致样品低温下的双相行为更加明显.添加Sn后引起样品中软磁相含量和软磁相晶粒尺寸的增加，使磁化反转中可逆磁化部分增多，且使反磁化形核场降低.磁黏滞性研究表明，热激活体积与软磁相晶粒的大小有关. 关键词： 纳米复合永磁 磁化反转 磁粘滞     

Oxygen vacancy‐induced microstructural changes of annealed CeO2−x nanocrystals

Nanocrystalline ceria (CeO₂) is known for its ionic conductivity and oxygen storage properties, which depend on the presence of oxygen ion vacancies. The vacancies cause several important changes in CeO₂ involving microstrain, electronic structure, magnetic properties, etc. In this article, we focus our attention to the microstructural changes of nanocrystalline CeO_2−x annealed at different temperatures in the range 200–500 °C. Structural and vibrational properties were investigated by X‐ray diffraction and Raman spectroscopy. It was observed that the content of oxygen vacancies changed significantly with increasing annealing temperature, which plays an important role in the observed microstructural changes of the annealed samples. We demonstrate that the observed microstrain changes, because of variable defect content, dominate over the crystallite size effect. This finding is opposite to the conclusions made by several other authors. A new mode, classified as a probable surface mode, was observed in the Raman spectra at ∼480 cm⁻¹, the appearance of which can be explained by the large defective structure and disorder in the ceria lattice. Copyright © 2011 John Wiley & Sons, Ltd.     

On the formation of the nanostructure in Fe80M7B12Cu1 (M: Ti, Ta, Nb, Mo) alloys

The dependence of the formation of the nanocrystalline bcc-Fe phase on the alloy composition is studied for Fe₈₀M₇B₁₂Cu₁ (M: Ti, Ta, Nb, Mo) alloys. The rf-Mössbauer technique is used to determine the optimal soft magnetic properties. This technique allowed us to compare anisotropy fields in each phase present in the composite alloys. The smallest anisotropy field was found in the bcc-Fe nanograins formed in Nb- and Mo-containing alloys.