A perturbed angular correlation spectrometer for material science studies

A four-detector perturbed angular correlation (PAC) spectrometer has been developed with ultra-fast BaF₂ detectors to acquire four coincidence spectra simultaneously, two at 180° and two at 90°. This spectrometer has double efficiency compared to that of a three-detector set-up. Higher efficiency is desirable for PAC studies in solid state physics where large number of coincidences are required to obtain the PAC spectra with good statistics and is particularly useful when the half-lives of the parent probe nuclei used for PAC measurements are ∼2–3 days or less as in ¹¹¹In (2.8 d), ⁹⁹Mo (2.7 d) and ¹⁴⁰La (1.7 d). The performance of the spectrometer has been tested for the HfO₂ monoclinic crystal in the temperature range from 77 to 873 K and for the HfF₄·3H₂O crystal at room temperature. The polycrystalline HfO₂ has been synthesized from Hf metal by heating in air. The hydrated hafnium fluoride has been crystallized by dissolving Hf metal in 40% HF and drying slowly at room temperature.      

Fluctuating Electric Field Gradients at 111Cd in Ice

¹¹¹Cd–PAC measurements have been made using the high specific activity of ¹¹¹In in the methanol–water mixtures of various concentrations at the room temperature. These experiments revealed that the perturbation factors 〈A ₂ G ₂〉 (integrated over two mean lives τ_N) do not follow the dependence of the macroscopic viscosity η. The observed dynamic character of the PAC spectra in ice is explained by the mobility of orientational and ionic defects. The activation energy for the diffusion process was determined to be E _a =0.35(1) eV. This revised version was published online in September 2006 with corrections to the Cover Date.     

Electric-field gradients at Ta donor impurities in Cr2O3(Ta) semiconductor

We report perturbed-angular-correlation (PAC) experiments on ¹⁸¹Hf(→¹⁸¹Ta)-implanted corundum Cr₂O₃ powder samples in order to determine the magnitude and symmetry of the electric-field gradient (EFG) tensor at Ta donor impurity sites of this semiconductor. These results are analyzed in the framework of ab initio full-potential augmented-plane wave plus local orbitals (FP−APW+lo) calculations. The results are also compared with EFG results coming from PAC experiments in isomorphous α-Al₂O₃ and α-Fe₂O₃ doped with ¹¹¹In→¹¹¹Cd and ¹⁸¹Hf→¹⁸¹Ta tracers. This combined analysis enables us to quantify the magnitude of the lattice relaxations induced by the presence of the impurity and to determine the charge state of the impurity donor level introduced by Ta in the band gap of the semiconductor.     

NH3在Ni/Pt(111)和Ni/WC(001)表面上分解的第一性原理研究

采用密度泛函理论和slab模型,研究NH₃在Ni单原子层覆盖的Pt（111）和WC（001）表面上的物理与化学行为,计算了Ni单原子覆盖表面的电子结构以及NH₃的吸附与分解.表面覆盖的单原子层中,Ni原子的性质与Ni（111）面上的Ni原子明显不同.与Ni（111）相比,Ni/Pt（111）和Ni/WC（001）表面上Ni原子dz²轨道上的电子更多地转移到了其它位置,该轨道上电荷密度降低有利于NH₃吸附.在Ni/Pt（111）和Ni/WC（001）面上NH₃吸附能均大于Ni（111）,NH₃分子第一个N-H键断裂的活化能则明显比Ni（111）面上低,有利于NH₃的分解,吸附能增大使NH₃在Ni/Pt（111）和Ni/WC（001）面上更倾向于分解,而不是脱附.N₂分子的生成是NH₃分解的速控步骤,该反应能垒较高,说明N₂分子只有在较高温度下才能生成.WC与Pt性质相似,但Ni/Pt（111）和Ni/WC（001）的电子结构还是有差异的,与Ni（111）表面相比,NH₃在Ni/Pt（111）表面上分解速控步骤的能垒降低,而在Ni/WC（001）上却升高.要获得活性好且便宜的催化剂,需要对Ni/WC（001）表面做进一步改进,降低N₂分子生成步骤的活化能.     

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

The active catalysts for methane formation from the gas mixture of CO₂ + 4H₂ with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO₂ prepared by calcination of aqueous ZrO₂ sol with Sm(NO₃)₃ and Ni(NO₃)₂. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO₂, and the activity for methanation increased by an increase in inclusion of Sm³⁺ ions substituting Zr⁴⁺ ions in the tetragonal ZrO₂ lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.     

Effect of Mg2+ on the Magnetic Compensation of Lithium–Chromium Ferrite

PAC measurements on ¹¹¹In(¹¹¹Cd) implanted and thermally treated α-Fe have shown an indication for a cubic defect with the ¹¹¹Cd probe in the centre of it. The measured room temperature (R. T.) magnetic hyperfine fields are B _hf1 = −38.4(8) T for substitution and B _hf2 = +11.5(3) T for the cubic defect. Additionally, probes with pure quadrupole frequency distributions were observed, which are incorporated in surface contaminations.     

Electric quadrupole interactions in nano-structured SnO 2 as measured with PAC spectroscopy

Measurements of the electric quadrupole interaction were used to characterize pure and cobalt-doped samples of SnO₂ prepared by the sol-gel method. Perturbed gamma–gamma angular correlation (PAC) spectroscopy using ¹¹¹In–¹¹¹Cd probe nuclei was employed for these measurements. A methodology was developed for sample preparation that were prepared by sol-gel method from pure metallic Sn (99.9999%) and Co (99.9998%) as starting materials. Carrier-free ¹¹¹In was added to the precursor sol-gel solution prior to the formation of gel. PAC measurements were carried out to follow the formation of the SnO₂. PAC measurements were carried out in the temperature range from 10 k to 1123 K and the results show that the electric quadrupole frequency depends on the annealing temperature.     

强耦合磁失措自旋冰系统Dy2Ti2O7单晶生长和基本磁性质测量

利用红外光源浮区法生长出大尺寸、高质量的磁失措自旋冰化合物Dy₂Ti₂O₇单晶体.X射线衍射实验证实晶体具有面心立方结构，空间群为Fd3m，晶胞参数a＝1.0112(2) nm，［111］和［400］方向X射线衍射摇摆曲线半高宽分别仅为0.07°和0.05°.直流磁化率与温度关系测量给出晶体的Van Vleck顺磁因子为2.46×10^-5 m³/mol，有效磁矩μ_eff＝10.24(4)μ_B，Cure-Weiss温度Θ_CW＝1.1 K，揭示Dy₂Ti₂O₇具有弱的铁磁性.对磁性起源的综合分析表明，该自旋冰晶体磁性质主要来源于磁偶极相互作用，且相关最近邻长程偶极相互作用能量标度D_nn＝3.00 K. 关键词： 2Ti₂O₇')" href="#">Dy₂Ti₂O₇ 浮区法晶体生长 关联电子系统 自旋冰     

Electric field gradients in Hf2Fe

Perturbed Angular Correlations (PAC) technique was applied to measure the electric field gradients (EFG) at ¹⁸¹Ta sites in Hf₂Fe. The compound has the cubic structure of the Ti₂Ni prototype with two non‐equivalent crystallographic sites for Hf atoms. EFGs for the two sites were measured as a function of the temperature. In addition, one more EFG was observed, which was assigned to the presence of defects in the lattice. The ratio of the measured EFG at the regular lattice sites has been used to assign charges to the ions through a simple calculation using the point charge model and it is shown that the lattice symmetry can explain the very different EFG at both sites. This revised version was published online in August 2006 with corrections to the Cover Date.     

Lattice Location Studies of Indium in Cr2O3

The lattice sites of implanted In atoms in Cr₂O₃ were investigated by means of electron emission channeling (EC) measurements using ¹¹¹In probe atoms. EC spectra were recorded for several axes and compared to simulations. Indium atoms are most likely located at near-Cr sites. Small differences in the EC patterns for prompt and delayed electrons may be an indication for displacements of ¹¹¹Cd emitter atoms following the electron capture decay of In. This revised version was published online in September 2006 with corrections to the Cover Date.     

NdNi2Ge2化合物的结构和电磁输运性质

利用非自耗真空电弧熔炼法制备了NdNi₂Ge₂化合物样品,采用X射线粉末衍射技术和Rietveld全谱拟合分析方法测定了其晶体结构. 结果显示该化合物的空间群为I4/mmm,点阵参数为:a=4.120(1),c=9.835(0),Z=2,Nd原子占据2a晶位,Ni原子占据4d晶位,Ge原子占据4e晶位. NdNi₂Ge₂化合物呈现顺磁性,应用居里-外斯定律拟合计算得到居里-外斯常数为25.8,居里-外斯温度为6.24 K. 有效势磁矩为3.69μ_B,这与理论计算Nd³⁺的磁矩相符,表明磁矩主要源于Nd³⁺. 电阻率变化范围为0.3 Ω ·μm^-1-1 Ω ·μm,电阻曲线拟合显示NdNi₂Ge₂呈半金属性. 关键词： 2Ge₂')" href="#">NdNi₂Ge₂ Rietveld结构精修 电磁输运     

Structural characteristics and morphology of SmxCe1−xO2−x/2 thin films

Effect of the deposition temperature (200 and 500 °C) and composition of Sm_xCe_1−xO_2−x/2 (x = 0, 10.9–15.9 mol%) thin films prepared by electron beam physical vapor deposition (EB-PVD) and Ar⁺ ion beam assisted deposition (IBAD) combined with EB-PVD on structural characteristics and morphology/microstructure was investigated. The X-ray photoelectron spectroscopy (XPS) of the surface and electron probe microanalysis (EPMA) of the bulk of the film revealed the dominant occurrence of Ce⁴⁺ oxidation state, suggesting the presence of CeO₂ phase, which was confirmed by X-ray diffraction (XRD). The Ce³⁺ oxidation states corresponding to Ce₂O₃ phase were in minority. The XRD and scanning electron microscopy (SEM) showed the polycrystalline columnar structure and a rooftop morphology of the surface. Effects of the preparation conditions (temperature, composition, IBAD) on the lattice parameter, grain size, perfection of the columnar growth and its impact on the surface morphology are analyzed and discussed.     

有机金属化学气相沉积法制备的Ni/Al2O3纳米复合材料的氢吸附

研究了通过有机金属化学气相沉积技术及单源分子前躯体方法制备的Ni/Al₂O₃纳米复合材料的氢吸附(存储). 在冷壁的有机金属化学气相沉积反应器中,通过降解Ni(acac)₂粉末基底上的[H₂Al(OtBu)]₂制备的Ni/Al₂O₃纳米复合材料. 通过X射线粉末衍射、扫描电镜、透射电镜以及能量色散型X射线荧光光谱等技术表征该复合材料. 采用自制Sievert's设备研究该复合材料的氢吸附(存储),可以储存约2.9%(重量比)的氢.     

NaREO2 (RE= Lu，Y) 的制备及其结构的研究

用高温固相法制备了NaLuO2和NaYO2晶体粉体.制备纯相的NaLuO2粉体晶体困难,而制备纯相NaYO2粉体晶体相对容易.为了测定NaLuO2产物中含少量Lu2O3不纯相的量,用X射线衍射绝标法确定了样品中这两者的重量比和谱峰比的关系,得到了绝标法常数kLu2O3关键词： 2')" href="#">NaLuO2 2')" href="#">NaYO2 2O3')" href="#">Lu2O3 XRD定量分析 稀土发光     

Surface chemistry and catalytic activity of Ni/Al2O3 irradiated with high-energy electron beam

The radiation effects induced effects by electron beam (EB) treatment on the catalytic activity of Ni/γ-Al₂O₃ were studied for the carbon dioxide reforming of methane with different EB energy and absorbed radiation dose. Transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to determine the change in structure and surface states of Ni/γ-Al₂O₃ catalyst before and after the EB treatment. Higher energy EB treatment is useful for increasing the proportion of the active sites (such as Ni⁰ and NiAl₂O₄-phase) on the surface. The increase of Ni/Al-ratio indicates that the Ni dispersion on the surface increased with the EB-treatment, resulting in an increase of the active sites, which leads to improving the catalytic activity. XPS measurement also showed a decrease of the surface carbon with EB dose. The maximum 20% increase in the conversion of CO₂/CH₄-mixture into CO/H₂ gas was observed for the catalyst treated with 2 MeV energy and 600 kGy dose of EB relative to untreated.     

Synthesis of ZnFe2O4 nanomagnets by Fe-ion implantation into ZnO and post-annealing

Fe ions of dose 8 × 10¹⁶ cm^-2 are implanted into a ZnO single crystal at 180 keV. Annealing at 1073 K leads to the formation of zinc ferrite (ZnFe₂O₄), which is verified by synchrotron radiation X-ray diffraction (SR-XRD) and X-ray photoelectron spectroscopy (XPS). The crystallographically oriented ZnFe₂O₄ is formed inside the ZnO with the orientation relationship of ZnFe₂O₄ (111)//ZnO (0001). Superconducting quantum interference device (SQUID) measurements show that the as-implanted and post-annealing samples are both ferromagnetic at 5 K. The synthesized ZnFe₂O₄ is superparamagnetic, with a blocking temperature (T_B = 25 K), indicated by zero field cooling and field cooling (ZFC/FC) measurements.     

Free Surface and Interface Thermodynamics of Liquid Nickel in Contact with Alumina

Sessile drop experiments of Ni and Ni(2at.%Al) were conducted under controlled working conditions, at 1500°C, P(O₂) 10^–9 Torr. It is shown that Al and oxygen atoms engaged in the capillary driven mass transport at the interface have a significant impact on the surface/interface thermodynamics. The surface energy of liquid Ni determined from experiments in which Ni comes into contact with Al₂O₃ is significantly lower than that of high purity Ni, due to the segregation of Al. The free energy of segregation of Al to the free surface of Ni ( G _S) was found to range from –164 to –152 kJ/mol, indicating a relatively strong tendency for segregation of Al to the free surface of Ni(Al). It is proposed that an Al(O)-rich liquid layer forms adjacent to the Ni-Al₂O₃ interface, which improves interfacial adhesion. In the Ni(Al)-Al₂O₃ system, an increase in the Al content of the alloy leads to the improvement of both wetting and adhesion of the alloy on the ceramic, correlating with the improvement in the interface strength after solidification.     

Study of hyperfine interactions in the intermetallic compound CePd2Si2 using PAC technique with 111Cd as probe nuclei

Perturbed γ???γ angular correlation spectroscopy (PAC) has been used to investigate the hyperfine interactions in the intermetallic compound CePd₂Si₂ using ¹¹¹In→¹¹¹Cd probe nuclei. Samples of CePd₂Si₂ were prepared by melting constituent elements in an arc furnace under pure argon atmosphere. Carrier-free ¹¹¹In nuclei were introduced into the samples by thermal diffusion at 800°C in vacuum during 12 h. The measurements were performed in the temperature range of 4.2–300 K. Above the magnetic transition temperature (T _N ?=?10 K), the results show two distinct and well defined quadrupole interactions that were assigned to probe nuclei occupying Ce and Si sites in the compound. The quadrupole frequencies were found to decrease linearly with increasing temperature. The PAC spectra taken below 10 K were analyzed with a model including combined electric quadrupole plus magnetic dipole interactions, from which the hyperfine magnetic field was determined.     

Co1-xNixSb3-ySey热电输运中晶界和点缺陷的耦合散射效应

结合机械合金化与放电等离子烧结工艺制备了Ni和Se共掺的细晶方钴矿化合物Co_1-xNi_xSb_3-ySe_y,研究了晶界和点缺陷的耦合散射效应对CoSb₃热电输运特性的影响.通过Ni掺杂优化载流子浓度提高功率因子.在x=0.1时,功率因子达到最大值1750μWm^-1K^-2(450℃),是没有掺Ni试样的两倍.晶界和点缺陷的耦合散射机理使晶格热导率急剧下降,其中Co_0.9Ni_0.1Sb_2.85Se_0.15的室温晶格热导率降低至1.67Wm^-1K^-1,接近目前单填充效应所能达到的最低值1.6Wm^-1K^-1,其热电优值ZT在450℃时达到最大值0.53.将Callaway-Von Baeyer点缺陷散射模型嵌入到Nan-Birringer有效介质理论模型,对晶界散射和点缺陷散射的耦合效应对热导率的影响进行了定量分析,模型计算与实验结果符合.理论模型计算表明,当晶粒尺寸下降到50nm同时掺杂引入点缺陷散射后,Co_0.9Ni_0.1Sb_2.85Se_0.15的晶格热导率下降到0.8Wm^-1K^-1. 关键词： 3')" href="#">CoSb₃ Ni和Se掺杂 热电性能 耦合散射效应     

Nuclear Spin Relaxation in Some Non-viscous Media Using the 181Hf Probe

Perturbed angular correlation (PAC) studies have been performed in liquid mercury, HCl media of different acid strengths, H₂O and H₃PO₄ using a ¹⁸¹Hf probe. It is found that, in case of H₂O, interaction between the nucleus and its excited atom following the β⁻ decay of ¹⁸¹Hf is a possible mechanism for the nuclear spin relaxation in this environment. In the liquid mercury and different acid media, however, the perturbations are found to arise due to molecular fluctuations.