汞在Ti2NO2 MXene表面吸附氧化的第一性原理计算

汞是一种有毒的重金属,在生产生活中以各种形式排放的汞对生态及人类健康都存在一定程度的威胁.因此,寻找高效的汞吸附剂具有十分重要的意义.本文基于密度泛函理论的第一性原理计算方法,研究了汞在Ti₂NO₂(MXene)和具有一个氧空位缺陷的Ti₂NO₂(Ov-Ti₂NO₂)上的吸附和氧化机理.计算结果表明Hg⁰在Ti₂NO₂表面的吸附为物理吸附,在Ov-Ti₂NO₂表面为化学吸附. Ti₂NO₂表面氧空位的存在可以改善HgO与Ov-Ti₂NO₂之间的相互作用,从而使吸附能提高116 kJ/mol. Hg⁰在Ov-Ti₂NO₂表面氧化为HgO的反应能垒为92.55 kJ/mol,小于其在Ti_2<...     

液态三元Ni-Cu-Fe合金比热的实验与计算研究

采用电磁悬浮落滴式量热方法测定了液态三元Ni₆₀Cu₂₀Fe₂₀合金在1436—2008K温度范围内的比热,实验获得的最大过冷度达232K(0.14T_L),结果表明比热值为33.27J·mol^-1·K^-1,并且随温度变化很小.在实验基础上,根据分子动力学方法结合嵌入原子势(EAM)和Quantum Sutton-Chen多体势(QSC)对比热进行了理论计算,揭示 关键词： 液态合金 比热 电磁悬浮 分子动力学计算     

Ti75Al25合金微观结构演变的分子动力学模拟

本文利用分子动力学模拟方法,研究了液态Ti₇₅Al₂₅合金在不同冷却条件下形成晶体及非晶的过程(Q1:1.0×10¹³K Ks^-1,Q2:1.0×10¹¹Ks^-1).利用平均原子体积、双体分布函数、键角分布函数、键对分析和Voronoi多面体方法研究了微观局域结构随温度的变化关系.研究发现:在Q1冷却过程中,液态Ti₇₅A1₂₅合金在1000 K发生玻璃化转变,形成非晶结构;而在Q2冷却过程中,液态Ti₇₅Al₂₅合金发生结晶,并最终形成hcp晶体结构.     

Ti-Al金属间化合物结构与性质的第一性原理模拟

采用软件CASTEP模拟Ti-Al金属间化合物的晶体结构、力学性质和电子性质.分析在0 K、0 GPa时,Ti-Al存在的四种热力学稳定结构：TiAl₃、TiAl₂、TiAl、Ti₃Al,发现TiAl₃、TiAl₂、TiAl可以看作由Al的面心立方结构衍化而来,而Ti₃Al的结构与Ti相似,为密排六方结构.随着Ti摩尔分数的增加,TiAl₃、TiAl₂、TiAl、Ti₃Al的体模量相当,剪切模量和Vickers硬度逐渐减小;Pugh比k值也逐渐减小,表示韧性逐渐变好.最后对态密度、Mulliken布居分析等进行模拟,发现这四种结构Ti-Al键都具有金属性、共价性及弱的离子性.     

Magnéli相亚氧化钛Ti8O15的电子结构和光学性能的第一性原理研究

采用基于密度泛函理论的平面波超软赝势法研究了Magnéli相亚氧化钛Ti₈O₁₅的电子结构和光学性能. 计算出的能带结构显示Ti₈O₁₅相比锐钛型TiO₂禁带宽度大幅度降低. 态密度分析表明, 其原因在于Ti₈O₁₅的O原子的2p轨道以及Ti原子的3p, 3d轨道相对于TiO₂的相应轨道向左产生了偏移, 同时由于O原子的缺失使得Ti原子的3d, 3p轨道多余电子在Fermi能级附近聚集形成新的电子能级. 态密度分析结果还显示, 相对于TiO₂, Ti₈O₁₅ Fermi能级附近电子格局发生了如下变化: O原子的2p轨道电子贡献减少, Ti原子的3d轨道的电子对Fermi能级贡献增大. 光吸收计算图谱表明, TiO₂仅在紫外光区有较高的光吸收能力, 而Ti₈O₁₅由于禁带宽度变窄引起光吸收范围红移到可见光区, 从而在紫外光区和可见光区都有较高的光吸收能力, 计算结果与实验得到的紫外-可见漫反射吸收光谱结果一致. 关键词： 第一性原理 8O₁₅')" href="#">Magnéli相亚氧化钛Ti₈O₁₅ 电子结构 光学性能     

KMgF3:Cr3+的EPR参量和K+空位研究

EPR和ENDOR表明:顺磁离子取代KMgF₃中的Mg²⁺离子后,所处的环境具有轴对称。本文研究了KMgF₃:Cr³⁺的Δg=g_∥-g_⊥和零场分裂值D,证实KMgF₃:Cr³⁺中K⁺空位的存在。并且指出:由于K⁺空位,使Cr³⁺的最近邻F^-离子分 关键词：     

新型红色荧光粉Sr2ZnMoO6:Sm3+的制备与发光性能

采用高温固相法合成了Sr₂ZnMoO₆:Sm³⁺新型红色荧光材料,并对其发光特性进行了研究。XRD测量结果表明所制备样品为纯相Sr₂ZnMoO₆晶体。样品的发射光谱由一系列锐谱组成,分别位于563 nm(⁴G_5/2→⁶H_5/2)、598 nm(⁴G_5/2→⁶H_7/2)、607 nm(⁴G_5/2→⁶H_7/2)和645 nm(⁴G_5/2→⁶H_9/2),最强发射为645 nm。样品激发光谱由电荷迁移带CT和Sm³⁺离子的特征激发峰组成,主激发峰位于284 nm(CT)和403 nm(⁶H_5/2-⁴L_13/2)。 随着Sm³⁺浓度的增大, Sr_2-xZnMoO₆:xSm³⁺材料的发光强度先增大后减小, 在x≥2%时,发生浓度猝灭现象。根据Dexter理论分析其猝灭机理为电偶极-电偶极相互作用。比较了Li⁺、Na⁺和K⁺作为电荷补偿剂的作用,发现均使Sr₂ZnMoO₆:Sm³⁺材料的发射强度得到增强,但以Li⁺补偿效果最为显著。     

Magnli相亚氧化钛Ti8O15的电子结构和光学性能的第一性原理研究

采用基于密度泛函理论的平面波超软赝势法研究了Magneli相亚氧化钛Ti8O15的电子结构和光学性能.计算出的能带结构显示Ti₈O₁₅相比锐钛型TiO₂禁带宽度大幅度降低.态密度分析表明,其原因在于Ti₈O₁₅的O原子的2p轨道以及Ti原子的3p,3d轨道相对于TiO₂的相应轨道向左产生了偏移,同时由于O原子的缺失使得Ti原子的3d,3p轨道多余电子在Fermi能级附近聚集形成新的电子能级.态密度分析结果还显示,相对于TiO₂,Ti₈O₁₅Fermi能级附近电子格局发生了如下变化:O原子的2p轨道电子贡献减少,Ti原子的3d轨道的电子对Fermi能级贡献增大.光吸收计算图谱表明,TiO₂仅在紫外光区有较高的光吸收能力,而Ti₈O₁₅由于禁带宽度变窄引起光吸收范围红移到可见光区,从而在紫外光区和可见光区都有较高的光吸收能力,计算结果与实验得到的紫外-可见漫反射吸收光谱结果一致.     

Sc掺杂Ti1–xNiSb半哈斯勒合金的制备与热电性能

采用高能球磨法制备了Ti_1-xNiSb(x=0,0.10,0.15,0.20,0.25)和Ti_1-x-ySc_yNiSb (x=0.10,0.15;y=0.03,0.05)样品,并系统地研究了Sc掺杂对Ti_1-xNiSb样品的物相、微结构以及电热输运性能的影响.实验结果表明,Sc掺杂能够有效降低载流子浓度,提高塞贝克系数,改善材料的电输运性能.此外,由于Sc掺杂能够提高原子间的结合能,从而有效减少了NiSb杂相.Ti_1-x-ySc_yNiSb的晶格热导率随Sc掺杂而上升,这可归因于化学键的增强以及电声散射作用的减弱.但是载流子浓度的急剧下降导致样品的电子热导率显著下降,从而Ti_1-x-ySc_yNiSb样品的总热,导率明显降低.最终,Ti_0.8Sc_0.05NiSb样品获得最佳的热电性能,其功率因子在973 K达到17.7μW·cm^-1·K^-2<...     

K离子掺杂增强NaErF4体系上转换发光

制备了一系列Na_1-xK_xErF₄@NaLuF₄的核壳纳米结构,核中K⁺掺杂摩尔分数变化范围为0%~8%。XRD分析结果揭示这些具有不同K掺杂浓度的纳米粒子均为β-相纳米结构。研究结果表明：随着K⁺浓度的增加,纳米结构中Er³⁺~650 nm处的红带发光强度呈现先增强后减弱的规律,当K⁺摩尔分数为4%时,Na_0.96K_0.04ErF₄@NaLuF₄纳米晶的发光强度达到最大,为未掺杂K⁺的NaErF₄@NaLuF₄纳米晶发光强度的3.7倍。其发光增强的原因在于K⁺的掺杂降低了Er³⁺微环境晶场宇称对称性,提高了Er³⁺离子⁴F_9/2→⁴I_5/2能级辐射跃迁几率,进而增强了Er³⁺的650 nm红带的上转换发光强度。     

μSR-Study of CeH2.7

Metallic CeH_2.7 shows a sizably increased electronic specific heat of γ=100 mJ/mol·K², compared to γ=0.04 mJ/mol·K² in LaH_2.7 at low tempratures, which could qualify it as another heavy electron system. μSR Knight shift and relaxation studies were started on a powderous CeH_2.7 sample in order to test this possibility further. It is found that the relaxation rate λ_T depends strongly on the applied field strength. These values indicate that the relaxation must be of electronic origin. Strong irreproducibilities at low temperature point to pronounced hysteretic features, which might be related to structural changes. The Knight shift shows a shallow peak around 150 K but no conspicious increase at low temperatures.     

Heavy electron behavior in a new uranium-based ternary compound: UPd2Sn

Electrical resistivity, magnetic susceptibility and specific heat measurements on a new compound, UPd₂Sn, reveal that this material exhibits valence fluctuation or Kondo lattice phenomena below a characteristic temperature ∼ 10 K. In particular, the electronic specific heat coefficient appears to be strongly temperature dependent with a maximum of ∼ 270 mJ/mole U−K² at 9.7 K and an extrapolated value of ∼ 70 mJ/mole U−K² at 0 K. The compound UPd₂Sn was expected to crystallize in the same structure as the family of cubic Heusler alloys, but instead, crystallized in a more complicated structure which appears to be orthorhombic. The compound can be characterized as a nonmagnetic, nonsuperconducting heavy electron material.     

Structural phase transitions in Pd0.8 Si0.2 and Pd0.75 Si0.20 Ag0.05 alloys observed by pac

The phase transition in the alloys Pd_0.8 Si_0.2 and Pd_0.75 Si_0.20 Ag_0.05 have been investigated through the quadrupole interaction of¹¹¹Cd impurities. The quadrupole interactions were measured by means of the TDPAC technique from room temperature up to about 870 K. The variation of the quadrupole interaction with temperature in the alloy PdSiAg shows aT ^3/2 dependence below and above 629 K, with coefficientsB=5.43(25)·10⁻⁵ K^−3/2 andB=3.70(15)·10⁻⁵ K^−3/2, respectively. This demonstrates that the alloy undergoes a phase transition around 629 K. The existence of two electric field gradients observed in the alloy PdSi,V _zz (1)=3.47(54)·10¹⁷ V/cm² andV _zz (2)=2.29(36)·10¹⁷ V/cm², indicates that there are two different¹¹¹Cd sites. The corresponding fractionsf ₁ andf ₂ strongly depend on temperature. Below 520 K, most¹¹¹Cd nuclei are subject to the higher EFGV _zz (1) (f ₁≈70%), whereas above 520 Kf ₁ falls rapidly to zero andV _zz (2) becomes dominant. The temperature dependences of thef ₁ andf ₂ reveal a picture of the phase transition between the two crystal structures.     

Low-temperature specific heat of USb and UTe

We have measured the low-temperature specific heat c_p of single-crystalline samples of USb and UTe between 0.1 and 12 K. From the experimental data we deduce values for the electronic specific-heat parameter γ of 0.2 mJ/mole K² and 10.3 mJ/mole K² for USb and UTe, respectively. c_p data below 1 K reveal the onset of nuclear specific heat with decreasing temperature. In our temperature range, this contribution is much stronger for USb than for UTe.     

Ab-initio study of long-period superstructures and anti-phase boundaries in Al-rich γ-TiAl (L10)-based alloys

In this work, we report first-principles investigation of structural stability of all experimentally observed ordered long-period superstructures (LPSs), viz., r-Al₂Ti, h-Al₂Ti, Al₅Ti₃ along with Al₅Ti₃′, Al₁₁Ti₇ and Al₃Ti₂ LPSs, which are observed only as short-range ordered clusters at nanoscale level in Al-rich TiAl-based alloys. We adopt a procedure based on space-filling tiling arrangement of ordered Ti₂Al, Ti₃Al, Ti₄Al motifs and their combination along with a symmetry analysis programme to determine the unit cell and the crystallographic information of Al₅Ti₃′, Al₁₁Ti₇ and Al₃Ti₂ LPSs in terms of L1₀ fcc unit cell. First-principles calculations are performed to further refine these crystallographic parameters (Wyckoff positions and lattice parameters) obtained from the above procedure. Moreover, it is found that the family of five LPSs have subgroup–supergroup relationships with γ-TiAl (Sp. gr. P4/mmm) and among themselves. Further, we find the inherent stability of r-Al₂Ti?+?γ-TiAl and 2Al₅Ti₃?+?γ-TiAl phase mixtures at 0?K compared to isomolecular Al₃Ti₂ and Al₁₁Ti₇ LPSs at their respective concentrations. The calculations of single-crystal elastic constants of Al₅Ti₃, Al₁₁Ti₇, Al₃Ti₂ and Al₅Ti₃′ LPSs show all these four structures are mechanically stable. We also calculate antiphase boundary (APB) formation energies for two types of APBs, viz., type-A and type-C in ordered Al₅Ti₃ LPS using the supercell approach. The relaxed APB energies for type-A and type-C APBs are 15.44 and 124.16?mJ/m², respectively.     

Structural,electronic and elastic properties of potassium hexatitanate crystal from first-principles calculations

The structural, electronic and elastic properties of potassium hexatitanate (K₂Ti₆O₁₃) whisker were investigated using first-principles calculations. The calculated cell parameters of K₂Ti₆O₁₃ including lattice constants and atomic positions are in good agreement with the experimental data. The obtained formation enthalpy (−61.1535 eV/atom) and cohesive energy (−137.4502 eV/atom) are both negative, showing its high structural stability. Further analysis of the electronic structures shows that the potassium hexatitanate is a wide-band semiconductor. Within K₂Ti₆O₁₃ crystal, the TiO bonding interactions are stronger than that of KO, while no apparent KTi bonding interactions can be observed. The structural stability of K₂Ti₆O₁₃ was closely associated with the covalent bond interactions between Ti (d) and O (p) orbits. Further calculations on elastic properties show that K₂Ti₆O₁₃ is a high stiffness and brittle material with small anisotropy in shear and compression.     

Titanium metallization of alumina ceramics by molten salt reaction

In this work, we reported a novel method that is flexible to metallize alumina ceramics with complex surface. Through Ti²⁺ disproportionation occurred in molten NaCl-KCl-K₂TiF₆ bath, the dense Ti layer was deposited on Al₂O₃ ceramics surface with strong adhesion. The effects of reaction temperature, time and initial K₂TiF₆ concentration on deposition rate were investigated. As-prepared coatings compose of bilayer structure of reactive Ti₂O phase, namely, the outer layer with coarse grains and the inner layer with fine grains. The wettability of eutectic Ag72Cu28 and Pb37Sn63 alloys with metallized Al₂O₃ ceramics was measured by using sessile drop method and compared with that of original ceramics. The results show that the metallized Al₂O₃ surface could be reactively wetted well with Ag72Cu28 and Pb37Sn63 alloys. The contact angles lowered to 35° and 8°, respectively, when temperature rose to 900 °C, showing significant enhancement of wettability after Ti metallization by molten salt reaction.     

A first principles calculation of site occupancy of the B2 phase in Ti2AlX (X=V,Cr, Fe,Mo, Ta,Nb, Zr,Hf and Re) intermetallics

The site occupancy of the B2 phase in Ti₂AlX (X=V, Cr, Fe, Mo, Ta, Nb, Zr, Hf and Re) intermetallics have been studied using first principles pseudo potential plane wave method.The Ti, Al and X atoms are arranged in five different ways, in the lattice sites corresponding to B2 structure of Ti₃Al. In Ti₃AlX, the X atoms are substituted at the Ti and / or Al sites. Further, the equilibrium lattice constants and the formation energy (E_for) of these intermetallics with different site occupancies in the B2 phase have been predicted. The formation energy values suggest that the B2 phase is stable in all alloys. Amongst the five cases in a particular alloy, stable configuration is identified with the minimum E_for and is further considered for the calculations of mechanical properties. All the alloys are mechanically stable in terms of Born stability criteria and show anisotropic behaviour. All the alloys display ductile behaviour in terms of G/B ratio.     

Structural and magnetic properties of Ti12M clusters (M=Sc to Zn)

The geometries, electronic, and magnetic properties of the 3d atom doped icosahedron (ICO) Ti₁₂M (M=Sc to Zn), where a dopant atom replaces either the centra l(Ti₁₂M^c) or surface (Ti₁₂M^s) Ti atom in ICO Ti₁₃ cluster, have been systematically investigated by using the density functional theory. The structures of all the optimized Ti₁₂M^c and Ti₁₂M^s clusters are distorted ICO. Sc, Ni, Cu, and Zn atoms prefer to displace surface Ti atom, V, Cr, Mn, and Fe atoms prefer to displace central Ti atom. The position of impurity atom depends on the strength of the interaction between the central atom and the surface atoms. As compared to the pure Ti₁₃ cluster, Ti₁₂M^c and Ti₁₂M^s (M=V, Fe, Co, and Ni) clusters are more stable, Ti₁₂M^c and Ti₁₂M^s (M=Sc, Cr, Mn, Cu, and Zn) are less stable. Both Ti₁₂Ni^s and Ti₁₂Ni^c are magic clusters, which originate from their electronic as well as geometric closed shells. Because the exchange interaction prevails over the crystal field in Ti₁₂M clusters, the valence electrons fill molecular orbitals in terms of Hund’s rule of maximum spin.     

SrRuO3的电子结构与磁性研究

用自洽的全势能线性丸盒轨道能带方法计算了氧化物体系SrRuO₃(SRO)的电子结构和磁性.对于理想的立方钙钛矿结构的计算得出的电子结构明显改善了已有的计算结果:每个元胞的磁矩为129μ_B,按原子球划分为084μ_B/Ru原子和011μ_B/O原子;Sr原子上的自旋磁矩几乎为零;费米能级处的态密度N(E_F)为435(states/Ryd/f.u.).关于实际的正交结构SRO,计算得出磁矩为108μ关键词： 过渡金属氧化物 电子结构 磁性