Wetting, Bonding and Interfacial Energy of Nanocrystalline Metal Particles on Crystalline DCH Polymer and Amorphous Carbon Substrates

Experimental results concerning the interaction between a variety of nanocrystalline metals (gold, silver, nickel and chromium) and both crystalline polymer [poly-DCH (1,6-di (N-carbazolyl)-2,4-hexadiene)] and amorphous carbon substrates, are presented and analyzed. Attention is focused on aspects of the interaction that concern interfacial bonding, its correlation with the cohesive energies of the various metals and the energy of the interfaces. Experimental contributions include qualitative estimates of the magnitude of interfacial energies for the crystalline polymer/metal and amorphous carbon/metal interfaces and a direct measurement of the interfacial energies for gold and silver nanocrystals deposited on the amorphous carbon substrate. The sequence of interfacial energy values for the polymer/metal and amorphous carbon/metal systems is also determined. The interfacial energies for both the poly-DCH and amorphous carbon substrates decreases in the order silver, gold, nickel, and chromium, as expected from cohesive energy, melting point and surface energy data for these elements. The crystalline polymer/metal interfaces were examined for the presence of orientation relationships using selected area diffraction and optical diffractometry of high-resolution TEM images. No orientation relationships were found for any of the polymer/metal combinations spanning a large range of metal reactivities. Lack of atomic matching or some as yet unknown surface condition on the polymer may be responsible for this effect.     

Mesoscopic and macroscopic dipole clusters: Structure and phase transitions

A two dimensional (2D) classical system of dipole particles confined by a quadratic potential is studied. This system can be used as a model for rare electrons in semiconductor structures near a metal electrode, indirect excitons in coupled quantum dots etc. For clusters of N ≤ 80 particles ground state configurations and appropriate eigenfrequencies and eigenvectors for the normal modes are found. Monte-Carlo and molecular dynamic methods are used to study the order-disorder transition (the “melting” of clusters). In mesoscopic clusters (N < 37) there is a hierarchy of transitions: at lower temperatures an intershell orientational disordering of pairs of shells takes place; at higher temperatures the intershell diffusion sets in and the shell structure disappears. In “macroscopic” clusters (N > 37) an orientational “melting” of only the outer shell is possible. The most stable clusters (having both maximal lowest nonzero eigenfrequencies and maximal temperatures of total melting) are those of completed crystal shells which are concentric groups of nodes of 2D hexagonal lattice with a number of nodes placed in the center of them. The picture of disordering in clusters is compared with that in an infinite 2D dipole system. The study of the radial diffusion constant, the structure factor, the local minima distribution and other quantities shows that the melting temperature is a nonmonotonic function of the number of particles in the system. The dynamical equilibrium between “solid-like” and “orientationally disordered” forms of clusters is considered.     

Fe39.4－xCo40Si9B9Nb2.6Cux纳米晶合金的有效磁各向异性研究

采用多晶材料趋近饱和定律研究了非晶Fe_39.4-xCo₄₀Si₉B₉Nb_2.6Cu_x(x=0.5,1,1.5) 合金在不同温度纳米晶化后的有效磁各向异性常数〈K〉.结果表明， Cu含量较低(x=0.5)时，纳米晶粒较大并且在较低的退火温度(550℃)下析出硬磁相，〈K〉随退火温度T_a升高显著增加；随着Cu含量的增加，有效地细化了晶粒，并且抑制了硼化物的析出，〈K〉明显减小.讨论了〈K〉与晶粒尺寸D及初始磁导率的关系. 关键词： 纳米晶 有效磁各向异性 磁导率 FeCo基合金     

高压烧结法合成致密纳米BaTiO3陶瓷结构和铁电性能研究

 在6 GPa压力、1 000 ℃温度条件下制备了致密的纳米BaTiO₃陶瓷，合成样品的平均晶粒尺寸为50 nm，理论密度在97%以上。通过介电测量，观察到了样品宽化的相变峰，它与粗晶陶瓷的相变峰大不相同。由于90°电畴的减少和退极化场的存在，观察到了细长的电滞回线，它是样品铁电性存在的有力证据，表明钛酸钡陶瓷的临界尺寸在50 nm以下。     

Sinter-active nanocrystalline CeO<Subscript>2</Subscript> powder prepared by a mixed fuel process: Effect of fuel on particle agglomeration

A modified combustion process, namely a mixed fuel process making use of a mixture of two fuels, such as citric acid and glycine has been developed to prepare nanocrystalline ceria powders. The effect of the mixed fuel and the different fuel to oxidant ratios on the decomposition characteristics of the gels were investigated by simultaneous thermal analysis experiments. It was established from various characterization techniques that the ceria powder prepared through the mixed fuel process has got the optimum powder characteristics, namely, a surface area of 33.33 m²/g and a crystallite size of 14 nm compared to the powders produced through the combustion process using a single fuel like glycine or citric acid. Such powders when sintered at 1250°C resulted in pellets with densities in the range of 94–96% of theoretical density. In this paper, we have carried out systematic studies on the sintering of ceria powders prepared by different approaches. The sintered ceramic from mixed fuel batch, exhibited and retained relative density more than 95% up to 1250°C and this data clearly underscores the ability of this process in developing ceria ceramics with increased stability against reduction.     

Anisotropic ferromagnetism induced in rutile single crystals by Co implantation

The magnetic and electrical properties of Co-implanted single crystalline TiO₂ rutile are presented. For fluences of the order of 10¹⁷ cm^-2 and implantation energy of 150 keV the maximum atomic concentration of cobalt is 13 at% at a depth of 65 nm from the surface. The as implanted single crystals exhibit superparamagnetic behaviour attributed to the formation of nanosized cobalt clusters. After annealing at 1073 K an anisotropic ferromagnetic behaviour emerges with the easy magnetization axis lying in the (001) plane of rutile. The ferromagnetic behaviour is associated with oriented cobalt aggregates. Electrical conductivity of the implanted samples annealed in vacuum also exhibits anisotropic behaviour at low temperatures, but no magnetoresistive effects were detected.     

Ferroelectric behaviour of 30nm BaTiO3 ceramics prepared by high pressure assisted sintering

Dense nanocrystalline BaTiO3 ceramics with a homogeneous grain size of 30 nm was obtained by pressure assisted sintering. The ferroelectric behaviour of the ceramics was characterized by the dielectric peak at around 120 ℃, the P-E hysteresis loop and some ferroelectric domains. These experimental results indicate that the critical grain size for the disappearance of ferroelectricity in nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering is below 30 nm. The ferroelectric property decreasing with decreasing grain size can be explained by the lowered tetragonality and the ＇dilution＇ effect of grain boundaries.     

Structural Analysis of Electroplated Amorphous-Nanocrystalline Ni-W

 Ductile nickel-tungsten (Ni-W) alloys containing about 20–21 at.%W were electroplated onto copper substrates. The development of the amorphous/nanocrystalline microstructure towards a complete crystallization by isochronal heat treatments in vacuum was monitored by different methods. For medium annealing temperatures a solid-solution of W in the fcc-Ni lattice was achieved resulting in an increased hardness. For temperatures of 600 °C and upward recrystallization started and thermodynamically stable intermetallic compounds like Ni₄W and NiW were formed. A third phase, containing more than 80 at.%W was also detected but could not be identified so far. Only by combination of different methods and especially by use of analytical TEM structural analysis and phase identification in these amorphous-nanocrystalline Ni-W alloys were successful.     

Structural characteristics and residual stresses in oxide films produced on Ti by pulsed unipolar plasma electrolytic oxidation

Oxide films, 7–10 µm thick, were produced on commercially pure titanium by plasma electrolytic oxidation in a sodium orthophosphate electrolyte using a pulsed unipolar current with frequency (f) and duty cycle (δ) varying within f = 0.1–10 kHz and δ = 0.8–0.2, respectively. The coatings comprised a mixture of an amorphous phase with nanocrystalline anatase and rutile phases, where the relative rutile content range was 17–25 wt%. Incorporation of phosphorus from the electrolyte into the coating in the form of PO₂ ^–, PO₃ ^2– and PO₄ ^3–, as demonstrated by EDX and FT-IR analyses, contributed to the formation of the amorphous phase. Residual stresses associated with the crystalline coating phase constituents were evaluated using the X-ray diffraction sin² ψ method. It was found that, depending on the treatment parameters, internal direct and shear stresses in anatase ranged from–205 (±17) to–431 (±27) MPa and from–98 (±6) to–145 (±10) MPa, respectively, whereas the rutile structure is comparatively stress-free.     

Symmetry based properties of the transition metal dichalcogenide nanotubes

The full geometrical symmetry groups (the line groups) of the monolayered, 2Hb and 3R polytypes of the inorganic MoS₂ and WS₂ micro- and nanotubes of arbitrary chirality are found. This is used to find the coordinates of the representative atoms sufficient to determine completely the geometrical structure of the tubes. Then some physical properties which can be deduced from the symmetry are discussed: electron band degeneracies, selection rules, general forms of the second rank tensors and potentials, phonon spectra. Received 13 April 2000