RESUMEN
Among friction modifier lubricant additives, molybdenum dialkyldithiocarbamate (MoDTC) provides excellent friction behavior in boundary lubricated tribocontacts. It is well established that the low friction obtained with MoDTC is as a result of the formation of lattice structure MoS2 nanosheets. However, the relationship between the molybdenum species quantity, its distribution on the contact surface, and the friction behavior is not yet fully understood. In this work, Raman microscopy and atomic force microscopy (AFM) have been used with the aim of understanding the link between the friction behavior and the MoDTC/ZDDP tribofilm formation and removal. Tribotests were coupled with a collection of ex-situ Raman intensity maps to analyze the MoS2 tribofilm buildup. Post-test AFM analyses were implemented on the ball wear scar to acquire the average MoDTC/ZDDP tribofilm thickness. In-situ Raman spectra analyses were carried out to detect the MoS2 tribofilm removal. A good correlation was achieved between the friction coefficient measurements and Raman maps when using a linear relationship between the microscopic friction and the local amount of MoS2 tribofilm. After a rapid increase, the average MoDTC/ZDDP tribofilm thickness levels out to a steady state as the friction drop ceases. The removal rate of MoS2 from tribofilms, obtained at different temperatures, suggests that the MoS2 tribofilms are much easier to remove from tribocontacts compared to antiwear ZDDP tribofilms. This is the first study that sets out a framework to link MoS2 amount and coverage to the friction behavior, providing the basis for developing numerical models capable of predicting friction by taking into account tribochemistry processes.
RESUMEN
The accurate determination of the mechanical properties of hydrogels is of fundamental importance for a range of applications, including in assessing the effect of stiffness on cell behaviour. This is a particular issue when using thin hydrogel layers adherent to stiff substrate supports, as the apparent stiffness can be significantly influenced by the constraint of the underlying impermeable substrate, leading to inaccurate measurements of the elastic modulus and permeability of thin hydrogel layers. This study used depth profiling nanoindentation and a poroelastic model for spherical indentation to identify the elastic moduli and hydraulic conductivity of thin polyacrylamide (PAAm) hydrogel layers (â¼27 µm-782 µm thick) on impermeable substrates. The apparent stiffness of thin PAAm layers increased with indentation depth and was significantly greater than those of thicker hydrogels, which showed no influence of indentation depth. The hydraulic conductivity decreased as the geometrical confinement of hydrogels increased, indicating that the fluid became more constrained within the confinement areas. The impact of geometrical confinement on the apparent modulus and hydraulic conductivity of thin PAAm hydrogel layers was then established, and their elastic moduli and intrinsic permeability were determined in relation to this effect. This study offers valuable insights into the mechanical characterisation of thin PAAm hydrogel layers used for the fundamental study of cell mechanobiology.
Asunto(s)
Hidrogeles , Módulo de Elasticidad , Hidrogeles/química , Biofisica , Conductividad EléctricaRESUMEN
The measurement of the elastic modulus of soft biomaterials via nanoindentation relies on the accurate determination of the zero-point of the tip-sample interaction on which the depth of penetration into the sample is based. Non-cantilever based nanoindentation systems were originally designed for hard materials, and therefore monitoring the zero-point contact presents a significant challenge for the characterisation of very soft biomaterials. This study investigates the ability of non-cantilever based nanoindentation to differentiate between hydrogels with elastic moduli on the order of single kiloPascals (kPa) using a bespoke soft contact protocol and low flexural stiffness of instrument. Polyethylene glycol (PEG) hydrogels were fabricated as a model system with a range of elastic moduli by varying the polymer concentration and degree of crosslinking. Elastic modulus values were calculated using the Oliver-Pharr method, Hertzian contact model, as well as a viscoelastic model to account for the time-dependent behaviour of the gels. The stiffness measurements were validated by measuring cantilever beams with the equivalent flexural stiffness to that of the PEG hydrogels being tested. The results demonstrated a high repeatability of the measurements, enabling differentiation between hydrogels with elastic moduli in the single kPa to hundreds of kPa range.