ZnO micro/nanocrystals with different percentages of the exposed (0001) facets were synthesized by a facile chemical bath deposition method. Various characterizations were carried out to understand the relationship between particle shape, exposed (0001) facets, and catalytic activity of ZnO nanocrystals for the thermal decomposition of ammonium perchlorate (AP). An enhancement in the catalytic activity was observed for the ZnO micro/nanocrystals with a higher percentage of the exposed (0001) facets, in which the activation energy E a of AP decomposition was lowered from 154.0 ± 13.9 kJ/mol to 90.8 ± 11.4 kJ/mol, 83.7 ± 15.1 kJ/mol, and 63.3 ± 3.7 kJ/mol for ZnO micro/nanocrystals with ca. 18.6%, 20.3%, and 39.3% of the exposed (0001) facets. Theoretically evidenced by density functional theory calculations, such highly exposed (0001) facets can be favorable for the adsorption and diffusion of perchloric acid, and also facilitate the formation of active oxygen which can lead to the oxidation reaction of ammonia more completely in the catalytic decomposition of AP.
TiAlN/VN multilayer coatings exhibit excellent dry sliding wear resistance and low friction coefficient, reported to be associated with the formation of self-lubricating V2O5. To investigate this hypothesis, dry sliding ball-on-disc wear tests of TiAlN/VN coatings on flat stainless steel substrates were undertaken against Al2O3 at 25 0 C, 300 0 C and 635 0 C in air. The coating exhibited increased wear rate with temperature. The friction coefficient was 0.53 at 25 0 C, which increased to 1.03 at 300 0 C and decreased to 0.46 at 635 0 C. Detailed investigation of the worn surfaces was undertaken using site-specific transmission electron microscopy (TEM) via focused ion beam (FIB) microscopy, along with Fourier transform infrared (FTIR) and Raman spectroscopy. Microstructure and triboinduced chemical reactions at these temperatures were correlated with the coating's wear and friction behaviour. The friction behaviour at room temperature is attributed to the presence of a thin hydrated tribofilm and the presence of V2O5 at high temperature.
Nano-structured TiAlCrYN coatings, grown by unbalanced magnetron sputtering on various steel substrates, exhibited friction coefficients 0.6-0.8 and wear coefficients 10 -16 -10 -15 m 3 N -1 m -1 in dry sliding wear tests. This article reports comprehensive worn surface analyses using SEM, TEM, EDX, EELS and Raman spectroscopy. A *80 nm thick tribofilm formed on the TiAlCrYN worn surface was found to have dense amorphous structure and homogeneous oxide composition of Cr 0.39 Al 0.19 Ti 0.20 Y 0.01 O 0.21 . Viscous flow of the amorphous tribofilm was dominant in causing the high friction coefficient observed. The coatings showed combined wear mechanisms of tribo-oxidation and nano-scale delamination.
Nano-scaled multilayered TiAlN/VN coatings have been grown on stainless steel and M2 high speed steel substrates at U B =-85 V in an industrial, four target, Hauzer HTC 1000 coater using combined cathodic steered arc etching/unbalanced magnetron sputtering. X-ray diffraction (XRD) has been used to investigate the effects of process parameters (Target Power) on texture evolution (using texture parameter T*), development of residual stress (sin 2 method) and nano-scale multilayer period. The composition of the coating was determined using energy dispersive X-ray analysis. The thermal behaviour of the coatings in air was studied using thermo-gravimetric analysis, XRD and scanning electron microscopy. The bi-layer period varied between 2.8 and 3.1 nm and in all cases a {1 1 0} texture developed with a maximum value T* = 4.9. The residual stress varied between-5.2 and-7.4 GPa. The onset of rapid oxidation occurred between 62 and 645 C depending on the (Ti+Al):V ratio. After oxidation in air at 550 C AlVO4, TiO2 and V2O5 phases were identified by XRD with the AlVO4, TiO2 being the major phases. The formation of AlVO4 appears to disrupt the formation of Al2O3 which imparts oxidation resistance to TiAlN based coatings. Increasing the temperature to 600 and 640 C led to a dramatic increase in the formation of V2O5 which was highly oriented (001) with a plate-like morphology. At 640 C there was no evidence of the coating on XRD. Increasing the temperature to 670C led to further formation of AlVO4 and a dramatic reduction in V2O5.
A 20-50 nm thick tribofilm was generated on the worn surface of a multilayer coating TiAlN/VN after dry sliding test against an alumina counterpart. The tribofilm was characterized by applying analytical transmission electron microscopy techniques with emphasis on detailed electron energy loss spectrometry and energy loss near edge structure analysis. Pronounced oxygen in the tribofilm indicated a predominant tribo-oxidation wear. Structural changes in the inner-shell ionization edges of N, Ti and V suggested decomposition of nitride fragments.
Grown by reactive unbalanced magnetron sputtering in a mixed N2 and CH4 gaseous medium, heterogeneous nanocomposite coatings in the Ti-Al-V-N-C system show extraordinarily excellent tribological performance of coated machining tools. Using analytical high resolution TEM, EELS, FEG-SEM, XRD, and Raman spectroscopy, this paper reports detailed structural and chemical characterization of the coatings grown at various CH4: N2 ratios. Meanwhile, the mechanical and tribological properties were also measured, including hardness, Young's modulus, residual stress and the dry-sliding friction and wear at varying environmental humidity. When CH4 gas was introduced in the deposition, the structure of the coatings has been found to experience a change from nano-scale TiAlN-VN multilayer architecture to a complex mixture of columnar grains of nc-TiAlV(N,C)/a-C nanocomposites and inter-column network of sp 2 -type amorphous carbon. Carbon incorporation and segregation also shows remarkable influence on the columnar growth model by leading to finer grain size. As compared to the carbon-free nitride coating, the nanocomposite coatings showed substantially reduced residual stress owing to the freecarbon precipitation, whereas the coatings maintained comparable hardness to the carbon-free TiAlN/VN. Their tribological properties were found to be strongly dependent on the environment. In humid air at RH > 30%, the coatings showed low friction coefficient less than 0.4 and extremely low wear rate at a scale of ~10 -17 m 3 N -1 m -1 .
A facile and rapid method for synthesizing single crystal gold spherical or platelet (nonspherical) particles is reported. The reaction takes place at the interface of two immiscible liquids where the reducing agent decamethylferrocene (DmFc) was initially added to hexane and gold chloride (AuCl) to an aqueous phase. The reaction is spontaneous at room temperature, leading to the creation of Au nanoparticles (AuNP). A flow focusing microfluidic chip was used to create emulsion droplets, allowing the same reaction to take place within a series of microreactors. The technique allows the number of droplets, their diameter, and even the concentration of reactants in both phases to be controlled. The size and shape of the AuNP are dependent upon the concentration of the reactants and the size of the droplets. By tuning the reaction parameters, the synthesized nanoparticles vary from nanometer to micrometer sized spheres or platelets. The surfactant used to stabilize the emulsion was also shown to influence the particle shape. Finally, the addition of other nanoparticles within the droplet allows for core@shell particles to be readily formed, and we believe this could be a versatile platform for the large scale production of core@shell particles.
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