RESUMEN
The distribution of metal aqua and chloro complexes is fundamental information for analysis of a chemical reaction involving these complexes. The present study investigated the speciation and structures of chromium aqua and chloro complexes using the thermodynamic model fitting analysis of UV-vis/X-ray absorption spectra. The existence of a negatively charged species was examined by adsorbability of chromium species on a strong base anion exchanger. In the results, a planar square [CrIII(H2O)4]3+, a planar square or distorted tetrahedral [CrIIICl(H2O)3]2+, a trigonal bipyramidal [CrIIICl3(H2O)2]0, and a distorted octahedral [CrIIICl4(H2O)2]- were confirmed and the thermodynamic parameters of complexation reactions were quantitatively determined. Investigation of the evolution of speciation of chromium aqua and chloro complexes in a pH 1 solution suggested the existence of [CrIIICl2(H2O) m ]+ (m = 2 or 3) during the hydration process, which diminished in the equilibrium state. The kinetic analysis deserves further investigation to understand the speciation process quantitatively.
RESUMEN
Co-Ni alloy nanoparticles, a potential candidate for microwave absorption material, were successfully synthesized by tuning the reduction timing of Co and Ni ions by introducing oleylamine as a complexing agent and 1-heptanol as a reducing solvent. The formation mechanism elucidated using time-resolved sampling and in situ X-ray absorption spectroscopy (XAS) and ultraviolet-visible (UV-vis) spectrophotometry measurements suggested that the delay in the reduction of Co ions via complexation with oleylamine facilitated the co-reduction of Co with Ni ions and led to the formation of Co-Ni alloys. The successful synthesis of Co-Ni alloys experimentally confirmed the differences in magnetic properties between alloy and core-shell structured Co50Ni50 particles. Further, the syntheses of Co-Ni alloys with different compositions were also possible using the above technique. In addition, the microwave absorption properties were measured using the free-space method utilizing a vector network analyzer of Co50Ni50âpolyethylene composite with different sheet thicknesses. A reflection loss (RL) value of -25.7 dB at 13.6 GHz for the alloy structure was more significant than the core-shell counterpart. The above values are high compared to results reported in the past. The validity of the measurements was confirmed by utilizing the parameter retrieval method to extract permittivity and permeability from the scattering parameter (S) and recalculation of the RL as a function of frequency.
RESUMEN
Recently, the development of bimetallic nanoparticles with functional properties has been attempted extensively but with limited control over their morphological and structural properties. The reason was the inability to control the kinetics of the reduction reaction in most liquid-phase syntheses. However, the alcohol reduction technique has demonstrated the possibility of controlling the reduction reaction and facilitating the incorporation of other phenomena such as diffusion, etching, and galvanic replacement during nanostructure synthesis. In this study, the reduction potential of straight-chain alcohols has been investigated using molecular orbital calculations and experimentally verified by reducing transition metals. The alcohols with a longer chain exhibited higher reduction potential, and 1-octanol was found to be the strongest among alcohols considered. Furthermore, the experimental evaluation carried out via the synthesis of metallic Cu, Ni, and Co particles was consistent with the theoretical predictions. The reaction mechanism of metallic particle formation was also studied in detail in the Ni-1-octanol system, and the metal ions were confirmed to be reduced via the formation of nickel alkoxide. The results of this investigation were successfully implemented to synthesize Cu-Ni bimetallic nanostructures (core-shell, wire, and tube) via the incorporation of diffusion and etching besides the reduction reaction. These results suggest that the designed synthesis of a wide range of bimetallic nanostructures with more refined control has become possible.
RESUMEN
Vacancy-mediated climb models cannot account for the fast, direct coalescence of dislocation loops seen experimentally. An alternative mechanism, self climb, allows prismatic dislocation loops to move away from their glide surface via pipe diffusion around the loop perimeter, independent of any vacancy atmosphere. Despite the known importance of self climb, theoretical models require a typically unknown activation energy, hindering implementation in materials modeling. Here, extensive molecular statics calculations of pipe diffusion processes around irregular prismatic loops are used to map the energy landscape for self climb in iron and tungsten, finding a simple, material independent energy model after normalizing by the vacancy migration barrier. Kinetic Monte Carlo simulations yield a self climb activation energy of 2 (2.5) times the vacancy migration barrier for 1/2ã111ã (ã100ã) dislocation loops. Dislocation dynamics simulations allowing self climb and glide show quantitative agreement with transmission electron microscopy observations of climbing prismatic loops in iron and tungsten, confirming that this novel form of vacancy-free climb is many orders of magnitude faster than what is predicted by traditional climb models. Self climb significantly influences the coarsening rate of defect networks, with important implications for post-irradiation annealing.