Coatings with a thickness from ~40 to ~50 µm on Ti6Al4V titanium alloy were formed by micro-arc oxidation in a silicate-hypophosphite electrolyte with additions of graphene oxide. Micro-arc oxidation treatment was carried out in the anode–cathode mode (50 Hz) with a ratio of anode to cathode currents of 1:1, a total density of 20 A/dm2, and a treatment duration of 30 min. The effect of the graphene oxide concentration in electrolytes on the thickness, roughness, hardness, surface morphology, structure, composition of micro-arc oxidation coatings, and its electrochemical corrosion behavior in 3.5% NaCl solution was studied. The input of graphene oxide additives into the base silicate hypophosphite electrolyte led to an increase in the hardness of micro-arc oxidation coatings. Electrochemical polarization studies and impedance data showed that the best characteristics in terms of corrosion-protective ability among coatings formed in electrolytes with graphene oxide additives were those formed in the electrolyte with a graphene oxide concentration of 0.1 g·L−l. A further increase in the graphene oxide concentration in the electrolyte did not improve the protective properties of micro-arc oxidation coatings.
For nanoparticle synthesis in a spark discharge, the influence of the degree of electrode asymmetry in the rod-to-rod configuration, using the example of silver electrodes, on the energy efficiency and nanoparticle composition is studied. The asymmetry degree was determined by the angle between electrodes’ end faces. Two types of discharge current pulses were used: oscillation-damped and unipolar, in which electrodes changed their polarities and had a constant polarity during a single discharge, respectively. A significant influence of the asymmetry degree of the electrode arrangement on the synthesized nanoparticle size, agglomeration and concentration, and on the synthesis energy efficiency, has been established. An increase in the degree of the electrode asymmetry with the oscillation-damped discharge current pulse led to an increased mass production rate and energy efficiency of nanoparticle synthesis, a significant fraction of which had large dimensions of more than 40 nm. The effect of the transfer of synthesized nanoparticles to the opposite electrode at the unipolar discharge current pulse led to the appearance of electroerosive instability, manifested in the formation of a protrusion on the anode surface, around which spark discharges, leading to its further growth and electrode gap closure.
Solvent-free aerosol jet printing has been investigated for fabricating metallic and semiconductor (gas-sensitive) microstructures based on copper nanoparticles on alumina, borosilicate glass, and silicon substrates. The synthesis of nanoparticles was carried out using a spark discharge directly in the printing process without the stage of preparing nano-ink. Printed lines with a width of 100–150 µm and a height of 5–7 µm were formed from submicron agglomerates consisting of primary nanoparticles 10.8 ± 4.9 nm in size with an amorphous oxide shell. The electrical resistivity, surface morphology, and shrinkage of printed lines were investigated depending on the reduction sintering temperature. Sintering of copper oxides of nanoparticles began at a temperature of 450 °C in a hydrogen atmosphere with shrinkage at the level of 45–60%. Moreover, aerosol heat treatment was used to obtain highly conductive lines by increasing the packing density of deposited nanoparticles, providing in-situ transformation of submicron agglomerates into spherical nanoparticles with a size of 20–50 nm. Copper lines of spherical nanoparticles demonstrated excellent resistivity at 5 μΩ·cm, about three times higher than that of bulk copper. In turn, semiconductor microstructures based on unsintered agglomerates of oxidized copper have a fairly high sensitivity to NH3 and CO. Values of response of the sensor based on non-sintered oxidized copper nanoparticles to ammonia and carbon monoxide concentration of 40 ppm were about 20% and 80%, respectively.
In this work, we have, for the first time, experimentally verified the hypothesis of reducing the agglomeration rate of aerosol nanoparticles produced by spark discharge upon decreasing the carrier gas temperature in the range of 24 °C to –183 °C. The synthesis of nanoparticles was implemented as a result of spark ablation of electrodes manufactured from Au with a purity of 99.998% installed in a specially designed gas chamber dipped into liquid nitrogen (−196 °C) to cool down the carrier gas supplied through one of hollow electrodes. It follows from the analysis of transmission electron microscopy images that both the average size of primary nanoparticles and the degree of their sintering become lower if the gas is cooled. For example, in the case of using nitrogen as a carrier gas, the average size of primary nanoparticles decreases from 9.4 nm to 6.6 nm as the gas temperature decreases from 24 °C to –183 °C. This also causes the aggregates to become more branched, manifested by the reduction in their solidity from 92% to 76%. The agglomeration model of Feng based on Smoluchowski theory was employed to calculate particle size distributions that were found to be consistent with the experimental data. The gold nanoparticles synthesized at room and cryogenic temperatures of the carrier gas (N₂, Ar + H₂, He) were used to pattern plasmonic nanostructures on ceramic alumina substrates by using aerosol jet printing technology for the purpose of demonstrating the possibility of their application in surface-enhanced Raman spectroscopy (SERS). The SERS enhancement factor was estimated at 2 × 106 from the analysis of SERS and normal Raman spectra of 1,2-bis(4-pyridyl)ethylene used as an analyte.
Germanium–tin nanoparticles are promising materials for near- and mid-infrared photonics thanks to their tunable optical properties and compatibility with silicon technology. This work proposes modifying the spark discharge method to produce Ge/Sn aerosol nanoparticles during the simultaneous erosion of germanium and tin electrodes. Since tin and germanium have a significant difference in the potential for electrical erosion, an electrical circuit damped for one period was developed to ensure the synthesis of Ge/Sn nanoparticles consisting of independent germanium and tin crystals of different sizes, with the ratio of the atomic fraction of tin to germanium varying from 0.08 ± 0.03 to 0.24 ± 0.07. We investigated the elemental and phase composition, size, morphology, and Raman and absorbance spectra of the nanoparticles synthesized under different inter-electrode gap voltages and the presence of additional thermal treatment directly in a gas flow at 750 °C. The research shows that the in-flow thermal treatment of aerosol-agglomerated nanoparticles produced special individual bicrystalline Janus Ge/Sn nanoparticles with an average size of 27 nm and a decreasing absorption function with a changing slope at 700 nm.
Aluminum nanoparticles attract scientific interest as a promising low-cost material with strong plasmon resonance in the ultraviolet region, which can be used in various fields of photonics. In this paper, for the first time, ultraviolet luminescence of zinc oxide nanoparticles in colloid solutions and nanostructure films in the presence of plasmonic aluminum nanoparticles 60 nm in size with a metal core and an aluminum oxide shell were studied. Mixture colloids of ZnO and Al nanoparticles in isopropyl alcohol solution with concentrations from 0.022 to 0.44 g/L and 0.057 to 0.00285 g/L, correspondingly, were investigated. The enhancement of up to 300% of ZnO emission at 377 nm in colloids mixtures with metal nanoparticles due to formation of Al-ZnO complex agglomerates was achieved. Plasmon nanostructures with different configurations of layers, such as Al on the surface of ZnO, ZnO on Al, sandwich-like structure and samples prepared from a colloidal mixture of ZnO and Al nanoparticles, were fabricated by microplotter printing. We demonstrated that photoluminescence can be boosted 2.4-fold in nanostructures prepared from a colloidal mixture of ZnO and Al nanoparticles, whereas the sandwich-like structure gave only 1.1 times the amplification of luminescence. Calculated theoretical models of photoluminescence enhancement of ideal and weak emitters near aluminum nanoparticles of different sizes showed comparable results with the obtained experimental data.