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Surface free energy (SFE) is a property which depends on the chemical state and roughness of the surface and it is necessary to develop a reliable method to evaluate SFE value on a small area, taking into account these two different contributions. Today contact angle methods are the most used and they allow to evaluate the global mean value of SFE on areas of mm2 size. With these methods, it is not possible to evaluate the effects of roughness, surface defects, chemical contamination on SFE value. In addition, it is difficult to determine the surface free energy value on small components which have dimensions smaller than drop diameter. Nanoindentation and atomic force microscopy techniques provide alternative direct measurement methods to evaluate the SFE on small areas (on the order of μm2 or nm2) through a contact mechanism triggered by the contact of two bodies. In order to evaluate the adhesion properties, currently three models, Johnson- Kendall-Roberts, Maugis-Dugdale and Derjaguin-Muller-Toporov, use the value of pull-off force (force required to separate the indenter tip from the sample). All influences of surface morphology on SFE values are lost using these methods. In fact the adhesion value obtained refers to the energy balance between two conformal surfaces, which depends mainly on the morphology of the harder material (i.e., diamond tip). In this work we describe a new methodology for the SFE determination consisting in the modeling and quantitative evaluation of the interaction between the tip and sample surface during the approach phase in a nanoindentation test. During the test, the nanoindenter tip is attracted to the sample surface until the sample reaction forces become significant (in this case physical contact between two bodies is achieved). The SFE value is evaluated using experimental force of attraction and displacement of the nanoindenter spherical tip when it approaches the sample surface. In this method the sample surface is not altered by the tip, therefore unlike pull-off force method, it could be very useful to evaluate the actual SFE considering the effect of sample morphology (controlled roughness or pattern). [ABSTRACT FROM AUTHOR]

In the present paper, the effect of residual stress on the mechanical behavior of thin hard coatings has been investigated by a new methodology based on the combined use of focused ion beam (FIB) micro-machining techniques and nanoindentation testing. Surface elastic residual stress were determined by nanoindentation testing on Focused Ion Beam (FIB) milled micro-pillars. The average residual stress present in a 3.8 microm CAE-PVD TiN coating on WC-Co substrate was calculated by the comparison of two different sets of load-depth curves, the first one obtained at centre of stress relieved pillars, the second one on the undisturbed (residually stressed) surface. Results for stress measurement were in good agreement with the estimate obtained by XRD (sin2 psi method) analysis on the same sample, adopting the same elastic constants. In addition, nanoindentation on stress relieved pillars also allowed to perform a more accurate evaluation of elastic modulus and hardness of the coating. The effect of residual stress on crack propagation modes was quantitatively analyzed by high-load nanoindentation and application of energy methods for fracture toughness evaluation. It is found that compressive residual stress plays a relevant role in determining the fracture behavior and failure modes of the coating. Finally, Microstructural observations of the deformation mechanisms of the TiN coating were performed by TEM analysis on the cross section of the indentation, obtained by FIB lamella thinning. Results showed that plastic deformation at the nanoscale essentially occurs by formation of shear bands inside the columnar grains, independently of residual stress. A transition between intra-granular shear deformation and columnar grain sliding is also observed as a function of the applied load.

The depth profile of thin film layers on bulk substrate, avoiding the cross-sectioning of samples, is commonly performed by techniques such as X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectroscopy (SIMS). Techniques based on X-ray emission intensity measurements by energy dispersive spectroscopy (EDS), with conventional matrix or ZAF correction, are normally applied to cross-sectioned samples. This article compares XPS with surface X-ray intensity measurements by EDS, carried out with a more realistic X-ray generation and absorption model, known as the pi(rho Z) model. The pi(rho Z) approach has been adopted together with Monte Carlo simulation for the proper selection of SEM accelerating voltages, in conjunction with the analysis of SEM morphological images for thin film density correction. The method discussed hereafter and compared with the XPS technique, has advantages of higher lateral resolution, non-destructive elemental analyses, morphological visualization, low cost, and faster performance. This methodology has been followed to verify the layered structure of SnO2/metal-based gas sensors. X-ray intensities were measured using an EDS ultra-thin window detector. Two different porous layers, 25-nm thick of SnO2 and 10-nm thick of Cu, were detected, showing better agreement with their nominal thickness compared to results obtained using XPS measurements where porosity affects XPS data. If confirmed to be reliable and as effective as XPS depth profiling, this technique may be adopted for process quality control purposes.