Development of the method of production of the ultrafine macrohomogeneous composite powder

ABSTRACT

A method of ultrafine macro-homogeneous composite powder – B₄C–ZrO₂ production using a planetary mill was developed. From the macro-homogeneous composite high-density ceramics, B₄C–ZrB₂ was produced by the method of reactive sintering (in situ) at 2000°C under the pressure of 41–42?MPa. The effect of ZrO₂ grain size and of its distribution in the matrix on the consolidation parameters, and the microstructure of the obtained ceramics was studied.     

Stabilizing nanometer scale tip-to-substrate gaps in scanning electrochemical microscopy using an isothermal chamber for thermal drift suppression

The control of a nanometer-wide gap between tip and substrate is critical for nanoscale applications of scanning electrochemical microscopy (SECM). Here, we demonstrate that the stability of the nanogap in ambient conditions is significantly compromised by the thermal expansion and contraction of components of an SECM stage upon a temperature change and can be dramatically improved by suppressing the thermal drift in a newly developed isothermal chamber. Air temperature in the chamber changes only at ~.2 mK/min to remarkably and reproducibly slow down the drift of tip-substrate distance to ~0.4 nm/min in contrast to 5-150 nm/min without the chamber. Eventually, the stability of the nanogap in the chamber is limited by its fluctuation with a standard deviation of ±0.9 nm, which is mainly ascribed to the instability of a piezoelectric positioner. The subnanometer scale drift and fluctuation are measured by forming a ~20 nm-wide gap under the 12 nm-radius nanopipet tip based on ion transfer at the liquid/liquid interface. The isothermal chamber is useful for SECM and, potentially, for other scanning probe microscopes, where thermal-drift errors in vertical and lateral probe positioning are unavoidable by the feedback-control of the probe-substrate distance.     

Hot explosive compaction of aluminum-nickelide composites

Two series of nickel-coated aluminum (Al-Ni) powder compositions were consolidated to full or near-full density by a hot-explosive-compaction (HEC) technique. Mixtures of 78Al-22Ni at. pct (63Al-37Ni wt pct) or 39Al-61Ni at. pct (23Al-77Ni wt pct) were placed in cylindrical containers, preheated to a range of temperatures from ambient to 1000 °C, and once at a uniform temperature, explosively compacted into a 150-mm-long and 15-mm-diameter rod-shaped billet using a cylindrical detonation arrangement. The resultant billets were sectioned and prepared for examination by optical microscopy and scanning electron microscopy (SEM). Energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and microhardness measurements were used to characterize the billet morphology, structure, and chemical composition. Analysis revealed that depending on the preheating temperature, the initial Al-Ni composition transformed into several aluminum nickelide (Al-Ni) intermetallics. The onset and nature of the shock-induced transformation from the precursors into the products are discussed.     

Hot explosive compaction of aluminum-nickelide composites

Two series of nickel-coated aluminum (Al−Ni) powder compositions were consolidated to full or near-full density by a hot-explosive-compaction (HEC) technique. Mixtures of 78Al-22Ni at. pct (63Al-37Ni wt pct) or 39Al-61Ni at. pct (23Al-77Ni wt pct) were placed in cylindrical containers, preheated to a range of temperatures from ambient to 1000°C, and once at a uniform temperature, explosively compacted into a 150-mm-long and 15-mm-diameter rod-shaped billet using a cylindrical detonation arrangement. The resultant billets were sectioned and prepared for examination by optical microscopy and scanning electron microscopy (SEM). Energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and microhardness measurements were used to characterize the billet morphology, structure, and chemical composition. Analysis revealed that depending on the preheating temperature, the initial Al−Ni composition transformed into several aluminum nickelide (Al−Ni) intermetallics. The onset and nature of the shock-induced transformation from the precursors into the products are discussed.     

Quasi-steady-state voltammetry of rapid electron transfer reactions at the macroscopic substrate of the scanning electrochemical microscope

We report on a novel theory and experiment for scanning electrochemical microscopy (SECM) to enable quasi-steady-state voltammetry of rapid electron transfer (ET) reactions at macroscopic substrates. With this powerful approach, the substrate potential is cycled widely across the formal potential of a redox couple while the reactant or product of a substrate reaction is amperometrically detected at the tip in the feedback or substrate generation/tip collection mode, respectively. The plot of tip current versus substrate potential features the retraceable sigmoidal shape of a quasi-steady-state voltammogram although a transient voltammogram is obtained at the macroscopic substrate. Finite element simulations reveal that a short tip-substrate distance and a reversible substrate reaction (except under the tip) are required for quasi-steady-state voltammetry. Advantageously, a pair of quasi-steady-state voltammograms is obtained by employing both operation modes to reliably determine all transport, thermodynamic, and kinetic parameters as confirmed experimentally for rapid ET reactions of ferrocenemethanol and 7,7,8,8-tetracyanoquinodimethane at a Pt substrate with ～0.5 μm-radius Pt tips positioned at 90 nm-1 μm distances. Standard ET rate constants of ～7 cm/s were obtained for the latter mediator as the largest determined for a substrate reaction by SECM. Various potential applications of quasi-steady-state voltammetry are also proposed.     

New corrosion cast media and its ability for SEM and light microscope investigation

SEM of corrosion casts (CC) provides the opportunities to study the vessels and ducts in the phyllogenetic and ontogenetic (age‐related) settings, as well as the pathogenesis, compensation, and sanogenesis in different diseases and experimental models. Along with the refinement of SEM CC, the requirements toward casting media (CM) as nontoxicity, low viscosity, quick polymerization, resistance to corrosion solutions, availability, and so on, gradually has developed. We aimed to adapt the sets widely used in dental practice toward the modern requirements to the CC. The following ratio of the components of Protacryl‐M and Aycryl‐C sets were used for the preparation CM—0.25 g MAYCRYL Powder +0.08 g Benzoyl Peroxide +5.0 ml Protacryl‐M liquid component +0.2 Redont Colour (dye concentrate). The obtained solidifying mass was injected in the blood vessels and biliary ducts of the adult Wistar white rats. The SEM of CC of different organs’ vascular networks, as well as a biliary tract, reveals that offered CM excellently replicates the forms and branching features of studied tubular structures of all sizes and gives the adequate imprinting of their luminal surfaces. Besides, CM may provide the replication of perivascular spaces and give the casts having no analogous in the appropriate literature. The CM prepared by us perfectly reproduces all possibilities of famous rubbers widely used for the casting of different vascular–ductular structures. Besides, it presents the new implications, which should be implemented in the profound research of the connective‐tissue skeleton of different organs.     

Generalized theory for nanoscale voltammetric measurements of heterogeneous electron-transfer kinetics at macroscopic substrates by scanning electrochemical microscopy

Here we report on a generalized theory for scanning electrochemical microscopy to enable the voltammetric investigation of a heterogeneous electron-transfer (ET) reaction with arbitrary reversibility and mechanism at the macroscopic substrate. In this theory, we consider comprehensive nanoscale experimental conditions where a tip is positioned at a nanometer distance from a substrate to detect the reactant or product of a substrate reaction at any potential in the feedback or substrate generation/tip collection mode, respectively. Finite element simulation with the Marcus-Hush-Chidsey formalism predicts that a substrate reaction under the nanoscale mass transport conditions can deviate from classical Butler-Volmer behavior to enable the precise determination of the standard ET rate constant and reorganization energy for a redox couple from the resulting tip current-substrate potential voltammogram as obtained at quasi-steady state. Simulated voltammograms are generalized in the form of analytical equations to allow for reliable kinetic analysis without the prior knowledge of the rate law. Our theory also predicts that a limiting tip current can be controlled kinetically to be smaller than the diffusion-limited current when a relatively inert electrode material is investigated under the nanoscale voltammetric conditions.