Stabilization of Cubic Zirconia with Manganese Oxide

A directionally solidified eutectic (DSE) of MnO-ZrO₂ has been investigated using a variety of electron optical techniques. It is found that considerable MnO goes into ZrO₂ to form a substitutional solid solution. About 14 wt% of MnO is soluble in ZrO₂ close to the eutectic temperature. The solubility of ZrO₂ in MnO, however, is quite low, less than 0.50 wt%. Electron diffraction experiments indicate that ZrO₂ (MnO) has the cubic fluorite structure. Diffuse scattering, similar to other cubic zirconias (e.g., CaO, MgO stabilized zirconia), is also observed in manganese-stabilized zirconia. Diffuse scattering indicates the presence of oxygen vacancies and thus confirms the defect nature of the fluorite structure. Electron energy loss spectrometry (EELS) fine structure analysis of the Mn L₂₃ edge provided clear evidence that Mn is present as Mn²⁺ in Mn-stabilized cubic ZrO₂.     

Ultrarapid Phase Conversion in β"-Alumina Tubes

β"-Alumina, the electrolyte of choice of sodium/sulfur and sodium/metal chloride batteries and alkali-metal thermal-electric converters, was sintered from precursor phases to high β"-phase purity in less than 15 s from the onset of densification by rapid pass-through rf induction coupled plasma sintering. The maximum instantaneous shrinkage rate was 1.8%/s. The resistivity was measured to be 13.8 ± 1.4 Ω·cm. The rapid conversion found is a significant improvement over conventional processing of β"-alumina, which requires extended postsintering annealing times to obtain high β"-phase purity.     

Controlled Synthesis and Stability of Co@SiO2 Aqueous Colloids

Magnetic nanoparticles have emerged as an important class of functional nanostructures with potential applications of magnetic resonance imaging, drug targeting, and bio-conjugation. We have developed a modified sol–gel approach to synthesize stable and well-dispersed magnetic Co@SiO₂ nanoparticles with improved control over shell thickness and larger core diameters. These well-defined Co@SiO₂ core–shell nanoparticles exhibit useful magnetic properties, and the protective silica shell allows them to be surface modified for bioconjugation for various biomedical applications. The core–shell nanoparticles were characterized by transmission electron microscopy, energy-dispersive spectroscopy, elemental mapping, and the line compositional analyses to demonstrate that uniform individually isolated core–shell nanoparticles are obtained through the improved synthetic route.     

Low-energy interfaces in NiO-ZrO2(CaO) eutectic

Interphase interfaces in the directionally solidified eutectic (DSE) NiO-ZrO₂(CaO) have been investigated using transmission electron microscopy (TEM) techniques. Arguments are presented, based on extensive experimental results, to show that the observed interface plane, (111) NiO//(100) ZrO₂, corresponds to a minimum in interface energy. The possible relaxation events associated with this interface are identified with the aid of imaging and diffraction analyses. A recently introduced technique of convergent beam electron diffraction for a plan-view bicrystal is attempted in order to identify rigid body translation associated with this interface. Some of the difficulties associated with this technique are discussed. This paper is based on a presentation made in the symposium “Interface Science and Engineering” presented during the 1988 World Materials Congress and the TMS Fall Meeting, Chicago, IL, September 26–29, 1988, under the auspices of the ASM-MSD Surfaces and Interfaces Committee and the TMS Electronic Device Materials Committee.     

Design of single peptides for self-assembled conduction channels

Self-assembly of peptides provides the possibility of achieving relatively long range order on surfaces. These ordered peptides can also form channels that can be used as conduction channels. In the past, studies were focused on electron conduction through the secondary structure and amine bond of peptides and these restrict conduction of electrons over a short range (a few nanometers). In this work, we demonstrate the realization of electron conduction over a longer range of a few hundred nanometers via π-π stacking of the phenyl groups in the tyrosine residue of a single peptide. The peptide used in this work was designed with a phenyl ring for π-π stacking at one end and a carboxylic group at the other end for binding to aminopropyltriethoxysilane (APTES) treated silicon wafer. The distance between the peptides is controlled by a disulfide bond formed between neighboring cysteine residue and also by the amine groups of aminopropyltriethoxysilane. We demonstrate that the self-assembled peptide is conducting in the dry state over hundreds of nanometers, realizing the possibility of using peptide as a molecular wire.     

Facile scheme for fabricating solid-state nanostructures using e-beam lithography and solution precursors

We demonstrate a facile approach for site-specific fabrication of organic, inorganic, and hybrid solid-state nanostructures through a novel combination of electron-beam lithography (eBL) and spin coating of liquid and sol-gel precursors, termed soft eBL. By using eBL patterned resists as masks in combination with a low cost process such as spin coating, directed growth of nanostructures with controlled dimensions is achieved without the need for the costly and difficult process step of etching ceramics. The highly versatile nature of the scheme is highlighted through the fabrication of nanostructures of a variety of materials such as ferroelectric, optoelectronic, and conducting polymeric materials at different length scales and spatial densities on a multitude of substrates.     

Melt‐Centrifuged (Bi,Sb)2Te3: Engineering Microstructure toward High Thermoelectric Efficiency

Microstructure engineering is an effective strategy to reduce lattice thermal conductivity (κ_l) and enhance the thermoelectric figure of merit (zT). Through a new process based on melt‐centrifugation to squeeze out excess eutectic liquid, microstructure modulation is realized to manipulate the formation of dislocations and clean grain boundaries, resulting in a porous network with a platelet structure. In this way, phonon transport is strongly disrupted by a combination of porosity, pore surfaces/junctions, grain boundaries, and lattice dislocations. These collectively result in a ≈60% reduction of κ_l compared to zone melted ingot, while the charge carriers remain relatively mobile across the liquid‐fused grains. This porous material displays a zT value of 1.2, which is higher than fully dense conventional zone melted ingots and hot pressed (Bi,Sb)₂Te₃ alloys. A segmented leg of melt‐centrifuged Bi_0.5Sb_1.5Te₃ and Bi_0.3Sb_1.7Te₃ could produce a high device ZT exceeding 1.0 over the whole temperature range of 323–523 K and an efficiency up to 9%. The present work demonstrates a method for synthesizing high‐efficiency porous thermoelectric materials through an unconventional melt‐centrifugation technique.     

Orientation‐Dependent Intercalation Channels for Lithium and Sodium in Black Phosphorus

Black phosphorus (BP) with unique 2D structure enables the intercalation of foreign elements or molecules, which makes BP directly relevant to high‐capacity rechargeable batteries and also opens a promising strategy for tunable electronic transport and superconductivity. However, the underlying intercalation mechanism is not fully understood. Here, a comparative investigation on the electrochemically driven intercalation of lithium and sodium using in situ transmission electron microscopy is presented. Despite the same preferable intercalation channels along [100] (zigzag) direction, distinct anisotropic intercalation behaviors are observed, i.e., Li ions activate lateral intercalation along [010] (armchair) direction to form an overall uniform propagation, whereas Na diffusion is limited in the zigzag channels to cause the columnar intercalation. First‐principles calculations indicate that the diffusion of both Li and Na ions along the zigzag direction is energetically favorable, while Li/Na diffusion long the armchair direction encounters an increased energy barrier, but that of Na is significantly larger and insurmountable, which accounts for the orientation‐dependent intercalation channels. The evolution of chemical states during phase transformations (from Li_xP/Na_xP to Li₃P/Na₃P) is identified by analytical electron diffraction and energy‐loss spectroscopy. The findings elucidate atomistic Li/Na intercalation mechanisms in BP and show potential implications for other similar 2D materials.     

Imaging nanoparticles in cells by nanomechanical holography

Nanomaterials have potential medical applications, for example in the area of drug delivery, and their possible adverse effects and cytotoxicity are curently receiving attention. Inhalation of nanoparticles is of great concern, because nanoparticles can be easily aerosolized. Imaging techniques that can visualize local populations of nanoparticles at nanometre resolution within the structures of cells are therefore important. Here we show that cells obtained from mice exposed to single-walled carbon nanohorns can be probed using a scanning probe microscopy technique called scanning near field ultrasonic holography. The nanohorns were observed inside the cells, and this was further confirmed using micro Raman spectroscopy. Scanning near field ultrasonic holography is a useful technique for probing the interactions of engineered nanomaterials in biological systems, which will greatly benefit areas in drug delivery and nanotoxicology.