Biological tissues subjected to rubbing, such as the cornea and eyelid or articular cartilage, are covered in brushy, hydrated mucous structures in order to reduce the shear stress on the tissue. To mimic such biological tissues, we have prepared polyacrylamide (PAAm) hydrogels with various concentrations of un-cross-linked chains on their surfaces by synthesizing them in molds of different surface energies. The selected molding materials included hydrophilic glass, polyoxymethylene (POM), polystyrene (PS), polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE). After synthesis, demolding, and equilibration in water, the elastic modulus at the hydrogel surface decreased with increasing water contact angle of the mold. The softer, brushier surfaces did not completely collapse under compressive pressures up to 10 kPa, remaining better hydrated compared to their denser, cross-linked analogs. The hydrogels with brushier surfaces displayed an order of magnitude lower coefficient of friction than the cross-linked ones, which is attributed to the ability of their near-surface regions to retain larger amounts of liquid at the interface. The characteristic speed-dependent friction of the denser, cross-linked hydrogel surface is compared to the speed-independent friction of the brushy hydrogels and discussed from the perspectives of (elasto)hydrodynamic lubrication, permeability, and shear-induced hydrodynamic penetration depth.
Hydrogels are often used as model systems for articular cartilage due to similarities in their tribological properties. However, neither the structures nor the friction mechanisms of either system are fully understood. A key aspect of hydrogel lubrication is the nature of the polymeric structure at the surface, and the lubricating water film. A combination of neutron reflectometry and infrared spectroscopy is used to probe polymer volume fraction from the interface into the bulk hydrogel and its dependence on the molding material. The depth dependence of the polymer‐network density influences the compressibility of the hydrogel surfaces, as demonstrated by both atomic force microscopy (AFM)‐ and micro indentation. By changing molding materials, substantial differences in the gradient of polymer‐network density are observed with depth. The lower the volume fraction of polymer at the hydrogel surface, the more water it can maintain at its interface as a substantial water film that is stable even under static conditions. Such films render the hydrogel highly lubricious, with a speed‐independent friction coefficient of μ = 0.01, measured in gemini contact. This result provides experimental evidence that the presence of these highly lubricious water films is strongly dependent on the polymer‐network structure at the surface.
To understand the dissipative mechanisms in soft hydrogel lubrication, polyacrylamide (PAAm) hydrogels with two distinct surface structures were examined under various contact conditions. The characteristic speed-dependent friction of the selfmated, crosslinked hydrogel surfaces could be explained by hydrodynamic shearing of a thin water layer between two rather impermeable bodies. On the other hand, the frictional response of brushy hydrogel surfaces is dependent on the contact conditions and the level of surface hydration. In a migrating contact, brushy hydrogels showed low, speed-independent friction (µ ~ 0.01) likely due to a thick layer of shearing liquid trapped within the sparse surface network. In stationary contact, however, brushy hydrogel surfaces can partially exude water from the near-surface region over time, as shown by timeresolved Fourier-transform infrared (FTIR) spectroscopy. This is assumed to be reflected in a friction increase over time. Interfacial shearing appears to shorten the characteristic exudation times compared to those observed under static loading. Once fluid has been exuded, brushy surfaces were shown to reach similar friction values as their crosslinked analogs. The results thus indicate that the dominating dissipation mechanism during sliding at low contact pressures is shearing of the interfacial liquid film, rather than poro-elastic dissipation within the bulk. Maintenance of surface hydration is therefore crucial, in order to take advantage of the low friction of such systems.
Surface-initiated controlled radical polymerization mediated by a Cu0 plate (SI-Cu0 CRP) emerges as a versatile and efficient method for the functionalization of the exposed surfaces of hydrogels with a wide variety of polymer brushes. When a Cu0 plate is placed in contact with initiator-bearing hydrogel surfaces in the presence of ligand and monomer and under ambient conditions, it rapidly consumes dissolved oxygen from the reaction mixture, further acting as a source of catalyst and leading to the rapid growth of hydrogel-bound polymer chains. Three types of functional surfaces have been prepared as examples of the wide range of potential materials that can be synthesized in this way, including a hydrogel with a protective, hydrophobic surface, a lubricious hydrogel, as well as a hydrogel with thermally switchable frictional properties.
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