X-ray photoelectron spectra of cobalt compounds

The X-ray photoelectron spectra of a variety of cobalt(II) and cobalt(III) complexes have been investigated. Intense satellite lines were observed for the 2p, 3s and 3p peaks in the case of the high spin cobalt(II) compounds, but not for low spin cobalt(III) complexes. The satellites of the 2p levels are best explained as arising from shake-up processes, whereas those of the 3s and 3p levels are thought to arise largely from multiplet (exchange) splitting of the levels. Multiplet splitting of the 2p level is small and responsible for an increase in the doublet separation of the 2p_1/2, 2p_3/2 spin-orbit levels of the high spin cobalt(II) compounds. The chemical shifts for cobalt differ for the 2p, 3s and 3p levels of the high spin cobalt(II) compounds. Those of the 2p and 3p levels of diamagnetic cobalt(III) and low spin cobalt(II) complexes are equal. The difference in the case of the high spin cobalt(II) compounds is thought to be due to the presence of unpaired 3d electrons.     

Co膜中多次超快瞬态反射突变现象研究

飞秒激光泵浦瞬态热反射技术是研究金属薄膜超快动力学的有效手段,这种技术具有两大突出特点：首先,可以揭示飞秒激光激发的微观电、声子的传输过程是一个非平衡热输运过程。其次,反射率瞬态变化实验中电子运动的超短时间分辨可以用来研究热过程中电子的非平衡相互作用情况。利用磁控溅射真空镀膜技术,在玻璃衬底和硅衬底上蒸镀了不同厚度的Co单层膜,Cr,Co双层膜以及Ag,Co双层膜。利用飞秒激光瞬态反射技术研究了Co膜及其双层膜的瞬态反射率响应。结果表明,在同一厚度的Co膜样品上,施加不同的泵浦光功率时,Co膜内电子的加热时间与泵浦光功率的大小无关,均为0.1344 ps。而对于不同厚度的Co膜,电子的热化时间与薄膜厚度直接相关。此外,发现与以往研究结果不同的是,在泵浦光功率足够大时,玻璃衬底上的Co膜在飞秒激光脉冲泵浦下会出现两次或三次瞬态反射率下降现象,Co膜厚度决定了Co膜内瞬态反射率突变的次数,即Co膜内电子的超快动力学变化次数。     

Carbon nanotubes produced by tunneling of cobalt nanoparticles in carbon fibers

Carbon nanotubes (CNTs) have been produced by the tunneling of cobalt nanoparticles in carbon fibers that are derived from electrospun polyacrylonitrile (PAN) fibers. During annealing, the PAN fibers transform to a composite of cobalt nanodroplets and carbon fibers. Driven by the high chemical potential of wrinkled graphene platelets and amorphous carbon with respect to graphite, the cobalt nanodroplets are to tunnel in the carbon fibers. When cobalt nanodroplets have an elongated shape, carbon atoms dissolved in the droplets precipitate preferentially and completely at their lateral sides, producing perfect CNTs that form bulk structures.     

Na0．15（H3O）0．2CoO2·ωH2O的超导电性

最近发现的水合钴氧化物超导体在某些方面具有与高温超导体十分相似的性质．本文报道含有高浓度的水合氢离子的钴氧化物超导体的超导电性磁测量结果．通过对样品的M（H，T）的测量，得到了大致的H～T相图．最后还讨论了系统中可能存在的2D-3D转变．     

spin-lattice relaxation in cobalt-containing aluminophosphate molecular sieves

Phosphorus spin-lattice relaxation was studied in aluminophosphate molecular sieves containing various concentrations of either framework or non-framework cobalt. The behaviour of nuclear magnetisation in the presence of these paramagnetic centres was described successfully in the limit of no spin-diffusion. The diffusionless regime was strongly indicated with non-exponential magnetisation recovery and was therefore easy to recognise. According to the model, spin-lattice relaxation rates depend on the square of cobalt concentration. Measured relaxation rates agreed well with calculations if effective cobalt concentration was considered rather than the average one. The latter was obtained by bulk elemental analysis, while the former was extracted from cobalt concentration depth-profiles measured with Auger electron spectroscopy. These measurements indicated that in impregnated samples containing non-framework cobalt there could be much more cobalt near the crystal surface than within the crystal. Because high cobalt concentration can lead to an invisible phosphorus, only nuclei deep within the crystal contribute to the NMR signal. In such a case, the effective concentration is simply the concentration of cobalt far from the crystal surface. In our case, two impregnated samples with different bulk cobalt concentrations exhibited equal relaxation rates. Previously, such a case was misinterpreted as a case, in which nuclear spin-lattice relaxation was independent of cobalt concentration. AES measurements, however, revealed, that although average concentrations of the two samples were different by a factor of two, their effective concentrations were equal and thus in complete agreement with observed relaxation rates.     

spin-lattice relaxation in cobalt-containing aluminophosphate molecular sieves

Phosphorus spin-lattice relaxation was studied in aluminophosphate molecular sieves containing various concentrations of either framework or non-framework cobalt. The behaviour of nuclear magnetisation in the presence of these paramagnetic centres was described successfully in the limit of no spin-diffusion. The diffusionless regime was strongly indicated with non-exponential magnetisation recovery and was therefore easy to recognise. According to the model, spin-lattice relaxation rates depend on the square of cobalt concentration. Measured relaxation rates agreed well with calculations if effective cobalt concentration was considered rather than the average one. The latter was obtained by bulk elemental analysis, while the former was extracted from cobalt concentration depth-profiles measured with Auger electron spectroscopy. These measurements indicated that in impregnated samples containing non-framework cobalt there could be much more cobalt near the crystal surface than within the crystal. Because high cobalt concentration can lead to an invisible phosphorus, only nuclei deep within the crystal contribute to the NMR signal. In such a case, the effective concentration is simply the concentration of cobalt far from the crystal surface. In our case, two impregnated samples with different bulk cobalt concentrations exhibited equal relaxation rates. Previously, such a case was misinterpreted as a case, in which nuclear spin-lattice relaxation was independent of cobalt concentration. AES measurements, however, revealed, that although average concentrations of the two samples were different by a factor of two, their effective concentrations were equal and thus in complete agreement with observed relaxation rates.     

Soft X-ray absorption spectroscopy of titanium dioxide nanopowders with cobalt impurities

The charge states of the cobalt ions in TiO₂ nanopowders with the anatase lattice are studied by soft X-ray absorption spectroscopy. It is found that, at a low cobalt impurity concentration (1.8 at %), the cobalt ions with an oxidation state 2+ are mainly located in the tetrahedral (T _d ) environment of oxygen ions. Amorphous titanium dioxide exists on the sample surface before heat treatment. Annealing in vacuum or hydrogen leads to the enrichment of the nanoparticle surfaces with Co²⁺ ions, a change in the coordination of the remaining part of cobalt ions from octahedral to tetrahedral, stabilization of the anatase structure, and the disappearance of the amorphous phase. The crystal lattice of the samples with a relatively high cobalt concentration (12 at %) is distorted, and annealing does not cause the disappearance of the amorphous phase of TiO₂. Cobalt is reduced to its metallic state upon hydrogen annealing of the samples with a high cobalt concentration.     

The Application of Mössbauer Emission Spectroscopy to Industrial Cobalt Based Fischer–Tropsch Catalysts

The application of Mössbauer emission spectroscopy to study cobalt based Fischer–Tropsch catalysts for the gas-to-liquids process was investigated. It was shown that Mössbauer emission spectroscopy could be used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer–Tropsch catalysts. Oxidation was observed under conditions that are in contradiction with the bulk cobalt phase thermodynamics. This can be explained by oxidation of small cobalt crystallites or by surface oxidation. The formation of re-reducible Co³⁺ species was observed as well as the formation of irreducible Co³⁺ and Co²⁺ species that interact strongly with the alumina support. The formation of the different cobalt species depends on the oxidation conditions. Iron was used as a probe nuclide to investigate the cobalt catalyst preparation procedure. A high-pressure Mössbauer emission spectroscopy cell was designed and constructed, which creates the opportunity to study cobalt based Fischer–Tropsch catalysts under realistic synthesis conditions.     

PAR分光光度法测定钴和镍

进行了用PAR分光光度法同时测定钴和镍的研究。在pH=5的NaAc-HAc缓冲溶液中,钴和镍可与显色剂4-(2-吡啶偶氮)间苯二酚(PAR)的溶液形成稳定的络合物,络合物的吸收光谱重叠相互干扰,经过实验确定以508.0、568.0nm作为钴(Ⅱ)、镍(Ⅱ)的测量波长,应用双波长线性回归法可同时测定。方法简单、快速、灵敏度高。     

Preparation and characterization of cobalt-based nanostructured materials

Nano-sized cobalt clusters passivated by alkane-thiol molecules were obtained by the action of concentrated thiol solutions on micrometric cobalt particles. Thiol molecules caused an erosive process on the metal grains with the consequent formation of nano-sized metal debris and cobalt thiolate as by-product. The final material microstructure was composed by cobalt clusters embedded into a continuum cobalt thiolate matrix. Depending on the thiol molecule length, the material texture ranged from rubbery to waxy. These new types of nanocomposite materials were found to be crystalline, thermally stable up to ca. 300 ^°C, intensely red colored, and high hydrophobic. In addition, they generated polymeric structures when dissolved in non-polar solvents. Received 27 September 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: giancaro@unina.it     

彩色金刚石中过渡金属离子的谱学研究

过渡金属镍、钴和铁是高温高压法合成金刚石的常用触媒,已有研究表明：采用镍、钴作触媒所合成的金刚石中存在镍、钴离子,部分天然金刚石含有镍离子;镍、钴离子以替代方式或间隙形式进入金刚石的晶格,并能与杂质氮形成复合体。为了探寻彩色金刚石中过渡金属离子存在的谱学标志,确定镍、钴离子在彩色金刚石中的赋存状态,文章对6颗彩色天然与合成金刚石进行了扫描电镜-能谱、显微红外光谱、光致发光谱、电子顺磁共振谱(EPR)等测试研究。结果表明天然与合成的样品都具有与镍、钴有关的发光中心与EPR结构：包括西澳的蓝灰色天然金刚石中与镍有关的884.6 nm等发光中心,以及天然变色金刚石中与钴有关的发光中心。对各种谱学测试结果的综合分析,得出样品中存在镍、钴离子并与杂质氮形成各种Ni-N或Co-N复合体的结论,其中在天然金刚石中发现钴离子在该领域研究中尚属首次。     

氮气浮选Co(Ⅱ)-SCN~--MG~+三元体系光度法测定VB_(12)中钴的研究

在酸性条件下 ,N2 可将钴 -硫氰酸铵 -孔雀石绿三元体系浮选于甲苯中 ,利用这一特性本文建立了浮选测钴新光度法。本法灵敏度高 ( ε=1.80× 10 5L·mol-1· cm-1) ,选择性强 ,除 Cu2 +、Zn2 +外其余共存离子基本无干扰 ,精密度可靠 ( RSD=1.89% ) ,测定药品 VB12 中钴的含量 ,结果令人满意     

Increase in the magnetostrictive susceptibility of Tb0.3Dy0.67Ho0.03Fe2−x Co x alloys upon substitution of cobalt for iron

This paper reports on the results of investigations into the concentration dependences of the magnetostrictive susceptibility, the magnetostriction, the magnetization, and the Curie temperature for Tb_0.3Dy_0.67Ho_0.03Fe_2?x Co _x alloys upon substitution of cobalt for iron. It is revealed that the temperature of the spin-reorientation transition shifts toward room temperature with an increase in the cobalt content in the range 0 ≤ x ≤ 1.3. Substitution of cobalt for iron in the alloys leads to a decrease in the contribution of the 3d transition metal sublattice to the magnetic anisotropy owing to the opposite signs of the single-ion anisotropy constants for iron and cobalt. The decrease observed in the magnetocrystalline anisotropy compensated in both rare-earth and 3d transition metal sublattices is responsible for the high magnetostrictive susceptibility of the studied compounds at a high cobalt content (x = 1.3) in the room-temperature range.     

Electrical conductivity of Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O ferromagnetic films at low temperatures

The results of experiments on electrical conductivity and magnetic properties of thin cobalt-doped zinc oxide films are reported. The results indicate the predominance of the hoping conduction mechanism at low temperatures and the band mechanism at high temperatures. An increase in the cobalt concentration from 1.5 to 6.3 at % leads to the reduction of the electrical conductivity of the films. The contribution of hopping conduction to the conductivity increases due to a decrease in the crystallinity of the films and localization of a part of electron states upon an increase in the cobalt concentration. For cobalt-containing films, a hysteresis of the magnetic moment as a function of the magnetic field is observed. The dependence of the shape of the magnetization curves on the cobalt concentration is irregular. The paramagnetic contribution to the magnetic susceptibility increases with the cobalt concentration.     

Nanosized superparamagnetic precipitates in cobalt-doped ZnO

The existence of semiconductors exhibiting long-range ferromagnetic ordering at room temperature still is controversial. One particularly important issue is the presence of secondary magnetic phases such as clusters, segregations, etc. These are often tedious to detect, leading to contradictory interpretations. We show that in our cobalt doped ZnO films grown homoepitaxially on single crystalline ZnO substrates the magnetism unambiguously stems from metallic cobalt nano-inclusions. The magnetic behavior was investigated by SQUID magnetometry, X-ray magnetic circular dichroism, and AC susceptibility measurements. The results were correlated to a detailed microstructural analysis based on high resolution X-ray diffraction, transmission electron microscopy, and electron-spectroscopic imaging. No evidence for carrier mediated ferromagnetic exchange between diluted cobalt moments was found. In contrast, the combined data provide clear evidence that the observed room temperature ferromagnetic-like behavior originates from nanometer sized superparamagnetic metallic cobalt precipitates.     

电化学阴极沉积制备氧化钴/CNTs复合电极的准电容特性

采用电化学阴极沉积还原Co(NO3)2的方法制备了具有准电容特性的氧化钴电极材料,其比容量达到280 F／g,采用CNTs作为电极基体,在其表面均匀的沉积了纳米钴化镍颗粒并由此制备了氧化钴碳纳米管复合电极材料.采用循环伏安,恒流充放电,交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征．实验表明复合电极具有良好的电化学特性,CNTs基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在1 mol／L KOH电解液中比容量达到322 F／g且表现了良好的电化学可逆性．并分别采用氧化钴／CNTs复合电极作为正极,活性炭纤维作为负极制备了复合型电化学电容器,其工作电压达到1．4 V,电容器质量比容量达到47 F／g．在0．1 A／cm2放电时,复合型电容器的能量密度达到10 Wh／kg,兼具高能量特性和优良的大电流放电特性．     

Enhanced piezoelectric properties of sodium bismuth titanate (Na0.5Bi4.5Ti4O15) ceramics with B‐site cobalt modification

The piezoelectric properties of the cobalt‐modified sodium bismuth titanate (Na_0.5Bi_4.5Ti₄O₁₅, NBT) piezoelectric ceramics were investigated. The piezoelectric properties of NBT ceramics were significantly enhanced by cobalt modification. The Curie temperature T_C and piezoelectric constant d₃₃ for the 0.3 wt% cobalt‐modified NBT ceramics (NBT‐C3) were found to be 663 °C and 30 pC/N, respectively. Thermal annealing studies presented that the cobalt‐modified NBT ceramics possess stable piezoelectric properties, demonstrating that the cobalt‐modified NBT‐based ceramics are promising candidates for high temperature piezoelectric applications. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Correlation effects in 3d transition metals: Presence of a two-hole core-satellite in cobalt

Photoemission spectra of the 2p-level have been recorded from evaporated films of the 3d transition metals vanadium, chromium and cobalt. Structures on the high binding energy side of the spectra are observed; cobalt shows a weak satellite structure that resembles the well-known shakeup satellite in the nickel core level spectrum, only less intense, whereas the core level spectra of V and Cr only show satellites due to collective electron excitations.     

Strong dependence of the (100) surface composition of A 50-50 iron-cobalt monocrystalline alloy with ion bombardment and annealing

A decomposition of the overlapping iron and cobalt Auger transitions, using pure element experimental spectra, has been applied to the Auger analysis of a 50-50 iron-cobalt alloy. We have found that a linear combination of the pure element spectra reproduces quite accurately the alloy spectra in a wide range of surface composition. Using this method a high depletion in iron upon argon bombardment is observed and different recovering temperatures are found for iron and cobalt.     

聚晶金刚石复合体超高压液相烧结理论研究

 在对前人有关聚晶金刚石超高压烧结机理的综合分析与评价的基础上,通过对金刚石与不同组分的钴熔体相互作用规律,及金刚石从钴熔体中的结晶热力学与动力学的理论研究,提出了石墨优先金刚石“溶解”和金刚石石墨化“溶解”的观点,阐明了钴熔体的性质对金刚石（石墨）的浸润扩散溶解过程,以及金刚石再结晶析出过程的影响,认为在金刚石-钴烧结系统中存在三种主要烧结机构：颗粒重排,溶解-析出和聚晶固架形成机构。不同温度条件下不同碳含量钴熔体在烧结过程中,对于促进金刚石表面石墨化,进一步引起颗粒重排,实现sp³结构碳原子在金刚石颗粒间的有效迁移传递以及D-D直接结合等方面起到了十分重要的作用。根据上述金刚石超高压液相烧结理论的基本观点,可较合理地解释聚晶金刚石复合体（PDC）在超高压烧结过程中观察到的一些基本现象和实验事实。