A novel approach for the direct detection of oxidizing agents in aqueous solution is presented using diamond-like carbon (DLC) protected waveguides in combination with attenuated total reflectance (ATR) mid-infrared spectroscopy. Pulsed laser deposition was applied to produce high-quality DLC thin films on ZnSe ATR crystals with thicknesses of a few 100 nm. Scanning electron microscopy and X-ray photoelectron spectroscopy has been used to investigate the surface properties of the DLC films including the sp(3)/sp(2) hybridization ratio of the carbon bonds. Beside excellent adhesion of the DLC coatings to ZnSe crystals, these films show high chemical stability against strongly oxidizing agents. IR microscopy was utilized to compare differences in the chemical surface modification of bare and protected ATR waveguides when exposed to hydrogen peroxide, peracetic acid, and peroxydisulfuric acid. The feasibility of DLC protected waveguides for real-time concentration monitoring of these oxidizing agents was demonstrated by measuring calibration sets in a concentration range of 0.2-10%. Additionally, principal component regression has been applied to analyze multicomponent mixtures of hydrogen peroxide, acetic acid, and peracetic acid in aqueous solution. Due to high chemical stability and accurate monitoring capabilities, DLC protected waveguides represent a novel approach for directly detecting oxidizing agents in aqueous solution with promising potential for industrial process analysis.

Abstract. The mechanical and tribological behavior of physical vapor deposited coatings on soft substrate materials gains increasing interest due to economical and environmental aspects -e.g. substitution of steels by light-weight metals or polymers in transport vehicles. Nevertheless, such soft materials require surface protection against wear in tribological contacts. Single layer hard coatings deposited at room temperature are brittle with a relatively poor adhesion. Therefore, they should be better substituted by tough multilayer coatings of soft-hard material combinations. However, the mechanics of such multilayer coatings with several 10 nm thick bilayer periods is difficult and yet not well described. The presented work tries to fill the gap of knowledge by focusing both on mechanical investigations of hardness, adhesion, and wear and on microscopic elucidation of deformation mechanisms. In the paper 1 µm thick Ti/TiN multilayer stacks were deposited by magnetron sputtering on soft austenitic steel substrates at room temperature to prevent distortion of functional components in future applications. High hardness was found for 8 and 16 bilayer films with modulation ratio Ti:TiN = 1:2 and 1:4. This was attributed (with use of transmission electron microscopy) to stopping the crack propagation in thin Ti layers of the multilayer systems by shear deformation combined with different fracture mechanisms in comparison with that for the TiN single layers (edge cracks at the border of the contact area and ring cracks outside, respectively).

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The development of the model of the multistep nanoindentation test with Berkovich indenter, accounting for the residual stress distribution, is one of the aims of the present paper. The specimen is unloaded in the intervals between the deformation steps. Substrate, which is composed of a ferritic steel and biocompatible pulsed laser deposition TiN coating, is considered. The selection of the TiN was inspired by its perspective application as the coating for a constructional element of the heart prosthesis (blood chamber and aortic valves). Sensitivity analysis of the model predictions with respect to its parameters is presented in the present paper. The theory of elastic-plastic deformations is used in the finite element model, which simulates both loading and unloading phases, accounting for the real geometry of the indent. The main goal of the present paper was to inversely analyse the tests for coating/substrate system. Square root error between measured and predicted forces is the objective function in the analysis. Results of the inverse calculations, which are presented in the present paper, may be helpful in simulations of the behaviour of TiN deposited on substrate in various applications as bionanomaterials.

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Functionalization of surfaces is an important task for nanotechnology to add specially designed physico-chemical properties to materials. Besides chemical modification of surfaces, physical adaptations gain increasing interest. Thus, understanding the influences of film deposition on surface topography formation is the basis for future developments. For physical or chemical vapour deposited (PVD, CVD) films, structure zone models were developed, clearly showing the influences of temperature and vapour energy and, thus, surface and bulk diffusion on film structures based on four different structure zones. Generally, similar zones are also found in PVD coatings on polymeric substrates; However, due to restrictions in coating temperatures due to the thermal resistance of most polymers, the coating temperature is restricted to mostly 50˚C, excluding thermal activation of at least surface diffusion of inorganic materials (metals and their nitrides, oxides, carbides, etc.) and resulting in columnar growth with dome-shaped column tops. Additionally, the high difference in mechanical properties between "stiff" inorganic coatings and "flexible" polymers implicates stress-induced growth phenomena, resulting in wrinkling, cracking and finally the formation of a superseding structure, depending on substrate and film materials and the vapour energy of the deposition method.

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