GdN,GdP和GdAs的电子结构：第一性原理研究

用从头计算第一性原理对Gd-V化合物进行了电子结构与磁性的理论研究.计算的理论基础是密度泛函理论和局域(自旋)密度近似,并应用了相对论性LMTO-ASA计算方法.结果表明Gd-V的非自旋极化能带均为半金属特征.在进行宽能带的自能修正后GdN的非自旋极化能带是半导体行为(E_{g≈019eV).自旋极化的LSDA计算结果表明Gd-V均为半金属性的能带结构,即空带与价带有微弱的交叠.在布里渊区的X点和Γ点,分别有n型和p型色散的能带穿过费米面.对于GdN而言,它的上自旋子带为半金属能带,而下自旋子带却 关键词：}     

Highly Bright and Photostable Li(Gd,Y)F4:Yb,Er/LiGdF4 Core/Shell Upconversion Nanophosphors for Bioimaging Applications

Intense green‐emitting Li(Gd,Y)F₄:Yb,Er/LiGdF₄ core/shell (C/S) upconversion nanophosphors (UCNPs) with a tetragonal bipyramidal morphology are synthesized. The morphology and UC luminescence of the Li(Gd,Y)F₄:Yb,Er UCNPs are significantly affected by the Li precursors, and bright UC green‐emitting Li(Gd,Y)F₄:Yb,Er UCNPs with a tetragonal bipyramidal shape, i.e., UC tetragonal bipyramids (UCTBs), are synthesized using LiOH·H₂O as a Li precursor. A LiGdF₄ shell is grown on the Li(Gd,Y)F₄:Yb,Er UCTBs, and the C/S UCNPs exhibit 4.7 times higher luminescence intensity than core UCTBs. The C/S UCNPs show a high absolute UC quantum yield of 4.6% under excitation with 980 nm near infrared (NIR) light, and the UC luminescence from the C/S UCNPs is stable under continuous irradiation with the 980 nm NIR laser for 1 h. The hydrophobic surfaces of the as‐synthesized C/S UCNPs are modified to hydrophilic surfaces by using poly(acrylic acid) (PAA) for bioimaging applications. They are applied to human cervical adenocarcinoma (HeLa) cell imaging and SK‐MEL‐2 melanoma cell imaging and in vivo imaging, including subcutaneous and intramuscular imaging, and UC luminescence images with high signal‐to‐noise ratio are obtained. Furthermore, sentinel‐lymph‐node imaging is successfully conducted with the PAA‐capped Li(Gd,Y)F₄:Yb,Er/LiGdF₄ C/S UCNPs under illumination with NIR light.     

A High-Efficiency MRI Contrast Agent as well as a Tumor Therapeutic Agent

Inorganic/polymercore/shell nanoparticles (NPs) for theranostics have always attracted research interest due to their flexible composition and facile synthesis. Here, core/shell NPs are prepared with gadolinium hydroxide nanorods cores and Mn ion-doped polydopamine shells. After PEG modification, the relaxation rate of Gd(OH)₃@MnPDA-PEG NRs achieved 35 s⁻¹mm ⁻¹. The characterization results indicate that the predoping Mn ions obviously promote the effect of MRI compared with the nanorods without or with postdoping Mn ions, and the predoping method can effectively control the actual doping account of metal ions. Considering the toxicity, dopamine and manganese in molar ratio of 8:1 is finally chosen. Gd(OH)₃@MnPDA-PEG nanorods are conducted in vivo and in vitro imaging and therapeutic experiments. The results show that the nanorods has low biological toxicity, excellent magnetic resonance imaging effects, clear photoacoustic imaging, and photothermal therapy effects.     

Theoretical investigation on structural, magnetic and electronic properties of ferromagnetic GdN under pressure

The tight-binding linear muffin tin orbital (TB-LMTO) method within the local density approximation is used to calculate structural, electronic and magnetic properties of GdN under pressure. Both nonmagnetic (NM) and magnetic calculations are performed. The structural and magnetic stabilities are determined from the total energy calculations. The magnetic to ferromagnetic (FM) transition is not calculated. Magnetically, GdN is stable in the FM state, while its ambient structure is found to be stable in the NaCl-type (B₁) structure. We predict NaCl-type to CsCl-type structure phase transition in GdN at a pressure of 30.4 GPa. In a complete spin of FM GdN the electronic band picture of one spin shows metallic, while the other spin shows its semiconducting behavior, resulting in half-metallic behavior at both ambient and high pressures. We have, therefore, calculated electronic band structures, equilibrium lattice constants, cohesive energies, bulk moduli and magnetic moments for GdN in the B₁ and B₂ phases. The magnetic moment, equilibrium lattice parameter and bulk modulus is calculated to be 6.99 μ_B, 4.935 Å and 192.13 GPa, respectively, which are in good agreement with the experimental results.     

Synthesis and characteristics of nano-size sandwich structure (Y,Gd)BO3: Eu3+ phosphors

The sandwich structure core–shell–shell nanospheres SiO₂@(Y,Gd)BO₃:Eu³⁺@SiO₂ (SiO₂@YGB@SiO₂) have been synthesized by depositing YGB nanoparticles on silica core surface through the precipitation method, followed by sol–gel processing of tetraethoxysilane (TEOS) to form smooth silica shell over the surface of YGB. The phosphors were characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), transmission electronic microscope (TEM) and photoluminescence spectra. The results showed that the phosphors with spherical morphology can be produced easily by assembling the core–shell or core–shell–shell structure, and the XRD patterns indicated that the crystallinity of YGB is weakened due to the core–shell structure, which resulting from the local site symmetry of Eu³⁺ was decreased. The photoluminescence properties of the product are compared with those of the pure YGB, the core–shell structure SiO₂@YGB and YGB@SiO₂. The emission intensity, relative luminous efficiency and Red/Orange values of phosphors are increased in the order SiO₂@YGB@SiO₂>SiO₂@YGB>YGB@SiO₂>YGB; and the chromaticity coordinates of the phosphors are shifted from orange of pure YGB to red of SiO₂@YGB@SiO₂.     

钢铁材料中形变诱导相变超细化机理研究

通过计算机编程建立奥氏体相中12[1 1 0]刃位错、奥氏体相中非形变区和形变区奥氏体/铁 素体相界模型.用实空间的连分数方法计算了非形变区和形变区奥氏体/铁素体相界界面能， 计算了碳、氮及微合金元素在完整晶体及位错区引起的环境敏感镶嵌能，进而讨论形变过程 中铁素体形核的难易程度，碳、氮及合金元素在位错区的偏聚及析出与铁素体细化的关系. 计算结果表明：α-Fe易于在高密度位错区（形变带、亚晶界、晶界）形核，在奥氏体形变 过程中，就会大大提高α-Fe形核率，细化铁素体晶粒；碳、氮和微合金元素易于单独或共 同 关键词： 奥氏体/铁素体相界 刃位错 形变 晶粒细化     

Microstructure and tribological properties of TiN, TiC and Ti(C, N) thin films prepared by closed-field unbalanced magnetron sputtering ion plating

TiN, TiC and Ti(C, N) films have been respectively prepared using closed-field unbalanced magnetron sputtering ion plating technology, with graphite target serving as the C supplier in an Ar-N₂ mixture gas. Bonding states and microstructure of the films are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) in combination with transmission electron microscopy (TEM). The friction coefficients are measured by pin-on-disc test and the wear traces of deposited films are observed by optical microscope. Results show that the TiN film and Ti(C, N) film exhibit dense columnar structure while the TiC film exhibits a mixed microstructure of main nanocrystallite and little amorphous phases. The Ti(C, N) film has the highest microhardness value and the TiC film has the lowest. Because of small amount of pure carbon with sp² bonds existing in the film, the friction coefficients of Ti(C, N) and TiC multilayer films are lower than that of TiN film. In addition, the multilayer structure of films also contributes visually to decrease of friction coefficients. The TiC film has extremely low friction coefficient while the wear ratio is the highest in all of the films. The results also show that the Ti(C, N) film has excellent anti-abrasion property.     

新型金属间化合物Sm(TiFe)12的结构与磁性

SmTiFe_x(x的数值为8—11)可形成稳定的金属间化合物,经测定,晶体结构属于ThMn₁₂型四方结构,空间群为14/mmm,本文着重分析了Sm(TiFe)₁₂和Gd(TiFe)₁₂的结构和磁性。Sm(TiFe)₁₂具有很强的单轴磁晶各向异性,易磁化方向为c轴,居里温度610K。通过对Gd(TiFe)₁₂磁性的研究,进一步分析了在Sm(TiFe)₁₂中Sm和Fe次晶格的各向异性,实验结果表明,Sm和Fe次晶格都具有单轴磁晶各向异性,易磁化方向皆沿c轴。这是继Nd₂Fe₁₄B型永磁体以后发现的又一种具有单轴磁晶各向异性的三元稀土-铁金属间化合物。 关键词：     

Structural,magnetic, and electrical properties of Gd-doped BiFeO<Subscript>3</Subscript> nanoparticles with reduced particle size

Pure and Gd-doped BiFeO₃ nanoparticles have been synthesized by sol–gel method. The significant effects of size and Gd-doping on structural, electrical, and magnetic properties have been investigated. X-ray diffraction study reveals that the pure BiFeO₃ nanoparticles possess rhombohedral structure, but with 10% Gd-doping complete structural transformation from rhombohedral to orthorhombic has been observed. The particle size of pure and Gd-doped BiFeO₃ nanoparticles, calculated using Transmission electron microscopy, has been found to be in the range 25–15 nm. Pure and Gd-doped BiFeO₃ nanoparticles show ferromagnetic character, and the magnetization increases with decrease in particle size and increase in doping concentration. Scanning electron microscopy study reveals that grain size decreases with increase in Gd concentration. Well-saturated polarization versus electric field loop is observed for the doped samples. Leakage current density decreases by four orders by doping Gd in BiFeO₃. The incorporation of Gd in BiFeO₃ enhances spin as well as electric polarization at room temperature. The possible origin of enhancement in these properties has been explained on the basis of dopant and its concentration, phase purity, small particle, and grain size.     

银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

Synthesis,structure, and magnetic properties of iron and nickel nanoparticles encapsulated into carbon

Nanocomposites based on iron and nickel particles encapsulated into carbon (Fe@C and Ni@C), with an average size of the metal core in the range from 5 to 20 nm and a carbon shell thickness of approximately 2 nm, have been prepared by the gas-phase synthesis method in a mixture of argon and butane. It has been found using X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy that iron nanocomposites prepared in butane, apart from the carbon shell, contain the following phases: iron carbide (cementite), α-Fe, and γ-Fe. The phase composition of the Fe@C nanocomposite correlates with the magnetization of approximately 100 emu/g at room temperature. The replacement of butane by methane as a carbon source leads to another state of nanoparticles: no carbon coating is formed, and upon subsequent contact with air, the Fe₃O₄ oxide shell is formed on the surface of nanoparticles. Nickel-based nanocomposites prepared in butane, apart from pure nickel in the metal core, contain the supersaturated metastable solid solution Ni(C) and carbon coating. The Ni(C) solid solution can decompose both during the synthesis and upon the subsequent annealing. The completeness and degree of decomposition depend on the synthesis regime and the size of nickel nanoparticles: the smaller is the size of nanoparticles, the higher is the degree of decomposition into pure nickel and carbon. The magnetization of the Ni@C nanocomposites is determined by several contributions, for example, the contribution of the magnetic solid solution Ni(C) and the contribution of the nonmagnetic carbon coating; moreover, some contribution to the magnetization can be caused by the superparamagnetic behavior of nanoparticles.     

Synthesis and structures of Al–Ti nanoparticles by hydrogen plasma-metal reaction

Three kinds of Al–Ti nanoparticles (7.7, 27.8, and 42.6 at.% Ti) have been prepared from Al–65, Al–85, and Al–88 at.% Ti master alloys by hydrogen plasma-metal reaction, with average particle sizes of 30, 25, and 80 nm, respectively. The higher evaporation rate of Al than Ti resulted in the low Ti contents in the nanoparticles than those in the master alloys. Microscopy observation revealed that the primary nanoparticles are spherical in shape, and occur as chain aggregates of several individual nanoparticles due to the faster collision rate than the coalescence rate. All the Al–Ti nanoparticles contain amorphous alumina layers of about 2–3 nm in thickness surrounding the crystalline core. AlTi intermetallic nanoparticles were successfully produced for Al–27.8 at.% Ti, with a single crystal of AlTi in one chain aggregate. The composite nanoparticles of Al together with some Al₃Ti phases are prepared for Al–7.7 at.% Ti, with each phase in the individual particle of one chain aggregate. The composite nanoparticles of AlTi with some AlTi₃ were produced for Al–42.6 at.% Ti, with each phase in the individual particle of one chain aggregate. The formation mechanism of Al–Ti nanoparticles was interpreted in terms of phase transition and the effect of hydrogen.     

Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property

ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO₂ layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO₂ nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO₂ core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO₂ nanoparticles with thinner SiO₂ shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment.     

Large coercivity and small exchange bias in Mn3O4 / MnO nanoparticles

Core/shell structured Mn₃O₄/MnO nanoparticles were prepared by arc evaporating metallic manganese in air. These nanoparticles show unconventional exchange bias phenomena, in which the Curie temperature of the ferrimagnetic Mn₃O₄ is lower than the Néel temperature of the antiferromagnetic MnO. The exchange bias field in Mn₃O₄/MnO nanoparticles is much smaller than that in Mn₃O₄/Mn nanoparticles, due to the weak interfacial exchange coupling. The coercivity of the Mn₃O₄ phase in nanoscale is almost three times greater than that of the bulk Mn₃O₄.     

Gold decorated NaYF<Subscript>4</Subscript>:Yb,Er/NaYF<Subscript>4</Subscript>/silica (core/shell/shell) upconversion nanoparticles for photothermal destruction of BE(2)-C neuroblastoma cells

Gold decorated NaYF₄:Yb,Er/NaYF₄/silica (core/shell/shell) upconversion (UC) nanoparticles (~70–80 nm) were synthesized using tetraethyl orthosilicate and chloroauric acid in a one-step reverse microemulsion method. Gold nanoparticles (~6 nm) were deposited on the surface of silica shell of these core/shell/shell nanoparticles. The total upconversion emission intensity (green, red, and blue) of the core/shell/shell nanoparticles decreased by ~31% after Au was deposited on the surface of silica shell. The upconverted green light was coupled with the surface plasmon of Au leading to rapid heat conversion. These UC/silica/Au nanoparticles were very efficient to destroy BE(2)-C cancer cells and showed strong potential in photothermal therapy.     

Synthesis and characterization of hollow nanoparticles of crystalline Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>

Although Gd₂O₃ (gadolinia) nanoparticle is the subject of intense research interest due to its magnetic property as well as controllable emission wavelengths by doping of various lanthanide ions, it is known to be difficult to prepare monodisperse crystalline gadolinia nanoparticles because it requires high temperature thermal annealing process to enhance the crystallinity. In this article, we demonstrate the synthesis of hollow nanoparticles of crystalline Gd₂O₃ by employing poly(N-vinylpyrrolidone) (PVP) to stabilize the surface of Gd(OH)CO₃·H₂O nanoparticles and to successively form SiO₂ shell as a protecting layer to prevent aggregation during calcinations processes. Silica shells could be selectively removed after calcinations by a treatment with basic solution to give hollow nanoparticles of crystalline Gd₂O₃. The formation mechanism of hollow nanoparticles could be suggested based on several characterization results of the size and shape, and crystallinity of Gd₂O₃ nanoparticles by TEM, SEM, and XRD.     

Large scale synthesis of pinhole‐free shell‐isolated nanoparticles (SHINs) using improved atomic layer deposition (ALD) method for practical applications

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) as a new member of Raman technique garnered great attention among scientific community. In this work, we used an improved experimental setup to float the bare silver nanoparticles in air with the help of extraneous airflow, and used atomic layer deposition (ALD) method to coat ultra‐thin inert shell without pinholes. Under optimal conditions, we successfully prepared three kinds of SHINERS NPs (Ag@Al₂O₃, Ag@SiO₂ and Ag@TiO₂) in large quantity without pinholes. The ultra‐thin inert shell maintains the SERS activity of silver nanoparticles for long period of time. Transmission electron microscopy (TEM) images confirm the uniform coating of shell material on silver nanoparticles. Finally, the as‐prepared SHINs have been applied to detect various samples to demonstrate the applications. The presented ALD method offers a unique way to coat ultrathin shell (1–10 nm) on metal nanoparticles in large quantity (1–10 g) for practical applications. Copyright © 2015 John Wiley & Sons, Ltd.     

微波法合成红色长余辉发光材料Gd2O2S:Eu,Mg,Ti及其发光特性

用微波辐射法首次合成了Gd2O2S:Eu,Mg,Ti红色磷光化合物,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光分光光度计等对合成产物进行了分析和表征.结果表明:材料的晶体结构为六方晶系,与Gd2O2S的相同.颗粒的形貌为类球形,分散性较好,尺寸在1～2 μm之间.Gd2O2S:Eu,Mg,Ti的激发光谱呈带状,激发光谱主峰位于360 nm,另外在400,422,472 nm等处也有激发峰存在;发射光谱为线状光谱,归属于Eu3 的5DJ(J=0,1,2)到7FJ(J=O,1,2,3,4)的跃迁.随着Eu浓度的增加,位于蓝绿区的586,557,541,513,498,471,468 nm处的发射峰逐渐减弱,而主峰位于627 nm处的红光发射明显增强.当Eu浓度为6 mol%时,红光发射最强.Mg,Ti共掺杂可显著改善其余辉性质.     

Influence of correlation and temperature on the electronic structure of bulk and thin film GdN

The influence of correlation and temperature on the electronic structure of bulk and thin film GdN has been studied using the s-f model, which combines the one electron band structure with a many body procedure. The tight binding linear muffin tin orbital (TB-LMTO) method was used to obtain the one electron band structure of the system. The s-f exchange coupling constants for each band were obtained from the spin polarized band structure of the system using a mean field model. Correlation effects are found to be present in the system. However they are not sufficiently strong to cause a correlation induced splitting in the spectrum. Some bands of the thin films of GdN exhibit splitting at T=T_c and it is due to the combined effect of correlation and temperature. The conduction bands of both the bulk and the thin films of GdN exhibit a red shift with respect to temperature.     

Blue TiO_{2 -x}/SiO2 nanoparticles by laser pyrolysis

Composite TiSiOC nanoparticles with Ti/Si ratio varying in a very large range were prepared by laser pyrolysis of a gas–spray mixture of silane and titanium tetra-isopropoxide. The as-formed nanoparticle batches exhibit intense blue colours, varying from dark to light blue while the Ti/Si ratio increases. This blue colour is attributed to the formation of sub-stoichiometric TiOcompounds induced by the presence of reducing agents such as silicon-based radicals and carbon atoms in the reaction medium. The blue colour of the powders is stable for several months at room temperature in normal atmospheric conditions. Elemental analysis, specific surface area and pycnometry measurements, as well as Photon Correlation Spectroscopy allow determining the chemical composition and size of the as-synthesized nanoparticles as a function of the Ti/Si ratio. X-ray diffraction, transmission electron microscopy and IR spectroscopy have been used to analyse their chemical organisation, nanostructure and morphology. Mean grain size is found around 20 nm. The nanoparticles exhibit a core-shell structure TiO/SiO₂, with a core made of titania, surrounded by an amorphous shell, mainly of silica. Crystallites of anatase are present in the core with size increasing with the Ti/Si ratio. Annealing under air at 800°C induces the removal of carbon and the crystallisation of the powders with light beige to white colours.