The excitonic light emission of ZnO films have been investigated by means of photoluminescence measurements in ultraviolet-visible region. Exciton confinement effects have been observed in thin ZnO coatings with thickness below 20 nm. This is enhanced by a rise of the intensity and a blue shift of the photoluminescence peak after extraction of the adsorbed species upon annealing in air. It is found experimentally that the free exciton energy (determined by the photoluminescence peak) is inversely proportional to the square of the thickness while core-level binding energy is inversely proportional to the thickness. These findings correlate very well with the theory of kinetic and potential confinements.

Recently, a family of hard mono- and multilayer TiAlCrSiYN-based coatings have been introduced that exhibit adaptive behavior under extreme tribological conditions (in particular during dry ultrahigh speed machining of hardened tool steels). The major feature of these coatings is the formation of the tribo-films on the friction surface which possess high protective ability under operating temperatures of 1000 °C and above. These tribo-films are generated as a result of a self-organization process during friction. But the mechanism how these films affect adaptability of the hard coating is still an open question. The major mechanism proposed in this paper is associated with a strong gradient of temperatures within the layer of nano-scaled tribo-films. This trend was outlined by the performed thermodynamic analysis of friction phenomena combined with the developing of a numerical model of heat transfer within cutting zone based on the finite element method. The results of the theoretical studies show that the major physical-chemical processes during cutting are mostly concentrated within a layer of the tribo-films. This nano-tribological phenomenon produces beneficial heat distribution at the chip/tool interface which controls the tool life and wear behavior.Results of x-ray photoelectron spectroscopy studies indicate enhanced formation of protective sapphire- and mullite-like tribo-films on the friction surface of the multilayer TiAlCrSiYN/TiAlCrN coating. Comprehensive investigations of the structure and phase transformation within the coating layer under operation have been performed, using high resolution transmission electron microscopy, synchrotron radiation technique: x-ray absorption near-edge structure and XRD methods.The data obtained show that the tribo-films efficiently perform their thermal barrier functions preventing heat to penetrate into the body of coated cutting tool. Due to this the surface damaging process as well as non-beneficial phase transformation (formation of AlN hex phase) drastically diminishes within the layer of the adaptive coating. Micro-mechanical properties measurements performed at room and elevated temperatures show that the hardness of the multilayer TiAlCrSiYN/TiAlCrN coating appears stable to 500 °C and then drops a little at 600 °C but still remains high. It means that if the surface tribo-films can reduce actual temperature down to this level the coating underneath is able to efficiently withstand heavy loads under operation.

This paper generalizes the results of our research, which was aimed at the development of adaptive cutting tool coatings for high speed dry cutting, from the inception of the idea to complex multilayer coatings for processing tough metals. Typically, the streams of external energy and matter during high speed cutting are causing damage to the tool materials and to the hard, protective coatings through multiple mechanical and chemical processes including oxidation, however these oxidation processes could be used to improve the tools’ lifetime. The structure and the phase transformations on the wear surface in the nanostructured single layer and nanolaminated multilayer PVD coatings were investigated by a set of electron spectroscopy methods. The dynamics of the secondary phase formation on the various stages of tool life is demonstrated. The obtained results show that the enhancement of non-equilibrium processes during friction leads to a dominating formation of protective triboceramics on a base of sapphire-like, tungsten, and niobium polyvalent oxides with a structure which decisively improves the wear performance. The mechanisms of the formation of non-equilibrium protective oxides at high speed dry cutting and the non-equilibrium thermodynamics approaches for the tribooxidation description are discussed. Polyvalent metals and multilayer coatings provide a wider set of protective oxide nanofilms.

Atomic-scale, tribo-ceramic films associated with dissipative structures formation are discovered under extreme frictional conditions which trigger self-organization. For the first time, we present an actual image of meta-stable protective tribo-ceramics within thicknesses of a few atomic layers. A mullite and sapphire structure predominates in these phases. They act as thermal barriers with an amazing energy soaking/dissipating capacity. Less protective tribo-films cannot sustain in these severe conditions and rapidly wear out. Therefore, a functional hierarchy is established. The created tribo-films act in synergy, striving to better adapt themselves to external stimuli. Under a highly complex structure and non-equilibrium state, the upcoming generation of adaptive surface engineered nano-multilayer materials behaves like intelligent systems - capable of generating, with unprecedented efficiency, the necessary tribo-films to endure an increasingly severe environment.

Experimental investigations of nano-scale spatio-temporal effects that occur on the friction surface under extreme tribological stimuli, in combination with thermodynamic modeling of the self-organization process, are presented in this paper. The study was performed on adaptive PVD (physical vapor deposited) coatings represented by the TiAlCrSiYN/TiAlCrN nano-multilayer PVD coating. A detailed analysis of the worn surface was conducted using scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES) methods. It was demonstrated that the coating studied exhibits a very fast adaptive response to the extreme external stimuli through the formation of an increased amount of protective surface tribo-films at the very beginning of the running-in stage of wear. Analysis performed on the friction surface indicates that all of the tribo-film formation processes occur in the nanoscopic scale. The tribo-films form as thermal barrier tribo-ceramics with a complex composition and very low thermal conductivity under high operating temperatures, thus demonstrating reduced friction which results in low cutting forces and wear values. This process presents an opportunity for the surface layer to attain a strong non-equilibrium state. This leads to the stabilization of the exchanging interactions between the tool and environment at a low wear level. This effect is the consequence of the synergistic behavior of complex matter represented by the dynamically formed nano-scale tribo-film layer.