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61.
62.
Abstract Intracavity laser spectroscopy has been applied for investigation of absorption spectrum of HfCl molecule. In the region 560–700 nm 59 bands have been obtained. Rotational structure analysis of 0–0 band indicated that Hund's case (c) of angular moment coupling applied to this molecule. The molecular constants (cm?1) calculated for upper and ground electronic states are: ω′ = 353.05 cm?1, ω″ = 379.65 cm?1, B′=0.21486 cm?1 B″ = 0.21801 cm?1. 相似文献
63.
Phil Liebing Jorna Kalim Natalia Arefyeva Florian Oehler Mathias Wickleder Antonio Togni 《Angewandte Chemie (International ed. in English)》2019,58(25):8585-8588
Four complexes of MCl4 (M=Ti, Zr, Hf) with the hypervalent trifluoromethyl iodine reagent trifluoromethyl‐1,3‐dihydro‐3,3‐dimethyl‐1,2‐benziodoxole ( 1 ,=L) are described. With TiCl4, an I?O bond cleavage occurs, leading to the formation of the trifluoromethyliodonium alcoholate complexes [Ti2Cl6(L)4]Cl2 ( 2 a ) and Ti2Cl8(L) ( 2 b ). Reactions with ZrCl4 and HfCl4 form the complexes ZrCl4(L)2 ( 3 ) and HfCl4(L)2 ( 4 ), respectively, wherein the original I?O bond is retained and elongated compared to that in free 1 . Therefore, the reactivity of 1 can be easily and practically fine‐tuned by addition of different metal chlorides, following the order ZrCl4/HfCl4<TiCl4<2 TiCl4. Complexes 2 a , 3 , and 4 are remarkably bench‐stable forms of activated reagent 1 , while 2 b is readily accessible in situ. 2 a and 2 b represent the first “real” trifluoromethyliodonium reagents derived from iodanes, that is, with the I?O bond being completely cleaved. The new complexes were shown to be useful for the trifluoromethylation of para‐toluenesulfonate under aprotic conditions. 相似文献
64.
高纯铪由于具有独特的理化性质,在核反应堆、等离子切割机、光学元件等方面有着重要的应用。高纯铪中杂质的种类和含量会影响高纯铪的物理化学性能,应用中对高纯铪纯度的要求也越来越高,这就对高纯铪的分析检测技术提出了更高的要求。激光剥蚀-电感耦合等离子体质谱法(LA-ICP-MS)是激光剥蚀进样技术与电感耦合等离子体质谱联用,可以直接分析固体样品,并且方法前处理简单,可以避免样品前处理过程中引入杂质,是一项高效、快速、精密的分析技术,在环境、地质、冶金、燃料能源、材料、生物医药、考古等领域广泛应用。所以,激光剥蚀-电感耦合等离子体质谱法(LA-ICP-MS)是高纯金属杂质元素最佳检测方法之一。还未见有应用LA-ICP-MS于高纯铪样品的报道。用LA-ICP-MS对高纯铪中10种杂质元素(Al,Sc,Ti,Fe,Ni,Cu,Mo,Ag,Sn,W)进行定量分析。为了降低激光剥蚀过程中元素的分馏效应,提高信号灵敏度和稳定度,对激光剥蚀参数进行优化实验。确定了激光剥蚀的最优仪器参数为:氦气流量600 mL·min-1,激光能量90%,剥蚀孔径150 μm,激光扫描速度60 μm·s-1,激光脉冲频率20 Hz。经实验优化后的ICP-MS仪器工作参数为:RF功率1 450 W,射频匹配电压1.8 V,载气流量0.85 L·min-1,冷却器流量0.85 L·min-1,采样深度7.5 mm。在最优参数条件下,利用内控标样建立工作曲线,各杂质元素标准曲线的线性相关系数为0.993 6~0.999 8。采集载气空白的信号强度,平行测定11次,以3倍空白信号的标准偏差所对应的含量作为元素的检出限,得到各元素的检出限为0.001~0.08 μg·g-1。将高纯铪制成尺寸合适的样品,用硝酸洗去样品表面的氧化物,将其装入剥蚀池中,运用线扫描剥蚀方式,在最佳仪器工作条件下,对三个高纯铪样品中的10种杂质元素进行定量分析。实验结果显示,杂质元素含量为0.17~36.76 μg·g-1,相对标准偏差为1.4%~20%,精密度良好。以184W为例,将LA-ICP-MS法和ICP-MS法的测定结果进行t检验,三个样品的t值分别为2.14,1.64和2.11,均小于显著性水平为0.05时的临界值(t0.05, 12=2.18),说明LA-ICP-MS法和ICP-MS法的测定结果在置信度为95%时没有显著性差异,即正确度良好。所以,该方法正确度和精密度良好,可用于高纯铪中杂质的定量分析。 相似文献
65.
Stability and mechanical properties of various Hf-H phases: A density-functional theory study 下载免费PDF全文
We performe first-principles density functional theory calculations to investigate the stability and mechanical properties of various Hf Hx(0 ≤ x ≤ 1) phases. For pure Hf phases, the calculated results show that the HCP and FCC phases are mechanically stable, while the BCC phase is unstable at 0 K. Also, as for various Hf Hx phases, we find that H location and concentration could have a significant effect on their stability and mechanical properties. When 0 ≤ x ≤ 0.25, the HCP phases with H at(tetrahedral) T sites are energetically most stable among various phases. The FCC and BCC phases with H at T sites turn to be relatively more favorable than the HCP phase when H concentration is higher than 0.25. Furthermore, our calculated results indicate that the H solution in Hf can largely affect their mechanical properties such as the bulk moduli(B) and shear moduli(G). 相似文献
66.
67.
68.
Mahfoud Ziyad Rachid Ahmamouch Mohamed Rouimi Slimane Gharbage Jacques C. Vdrine 《Solid State Ionics》1998,110(3-4):311-318
Phosphates of general formula M0.5Hf2(PO4)3 with M=Cd2+, Ca2+, Sr2+ and Cu2+ were prepared by coprecipitation and characterized by several physical techniques. The compounds containing Cd2+, Ca2+, Sr2+ belong to the Nasicon-type structure, whereas Cu0.5Hf2(PO4)3 exhibited substantially different DRX patterns. Combined temperature programmed reduction (TPR) and temperature-programmed oxidation (TPO) showed that the copper in Cu0.5Hf2(PO4)3 was distributed between two energetically different sites in proportions respectively equal to 40 and 60%. Electron Paramagnetic Resonance (EPR) investigations confirmed the TPR/TPO results and revealed that the two sites hosting the Cu2+ ions are of orthorhombic symmetry. Moreover, the Cu2+ ions might be reduced by hydrogen to Cu+. These results were also supported by the UV–visible studies that showed the disappearance, under reducing conditions, of the band corresponding to crystal field transitions of Cu2+ ions and the emergence of a new peak attributed to the transitions between (3d)10 and (3d)9(4s)1 Cu+ levels. At the same time, IR spectroscopy confirmed that protons entered the open lattice framework of the material and gave rise to a new protonated phase containing monovalent copper Cu0.5IH0.5Hf2(PO4)3. This redox process was proven to be reversible without any subsequent change in the network of the phosphate. 相似文献
69.
Hydride formation was studied in the Hf2Fe−H2 system at hydrogen pressure of up to 2000 atm in a temperature range from 195 to 295 K. Hydride phases of different compositions
were studied by the X-ray diffraction method. The hydrogenation reaction in the system can take two pathways to form two stable
hydride phases depending on the conditions of initial hydrogenation. Absorption of hydrogens at a pressure of about 2000 atm
yields a hydride which contains two H atoms per metal atom. Models of the arrangement of hydrogen atoms in the crystal lattice
of hydride phases were suggested.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 33–36, January, 1997. 相似文献
70.
Cs2Cu3MIVF12 (MIV = Zr, Hf) – Crystal Structure and Magnetic Behaviour Colourless single crystals of Cs2Cu3ZrF12 are obtained by heating the binary fluorides in sealed Pt-tubes under dry argon (solid state reaction, T ≈? 700°C, t ≈? 7–10 d). The compound crystallizes trigonal-rhomboedrical in the space group R3 m-D (Nr. 166); lattice parameters are a = 716.61(6) pm, c = 2 046.4(2) pm, Z = 3 (Four cycle diffractometer data, AED 2). The structure is dominated by layers of corner-sharing, Jahn-Teller-distorted [CuF6]-Octahedra, which are connected via regular [ZrF6]-Octahedra to stackings parallel [00.1]. Cs+-ions are located in the spacings of the octahedra-network. From powder data Cs2Cu3HfF12 with a = 716.32(4) pm, c = 2 048.6(2) pm is isotypic. Both compounds show antiferromagnetic behaviour already at temperatures about 200 K. 相似文献