Controlling the Friction of Gels by Regulating Interfacial Oxygen During Polymerization.

Hydrogel surfaces are of great interest in applications ranging from cell scaffolds and transdermal drug-delivery patches to catheter coatings and contact lenses. In this work, we propose a method to control the surface structure of hydrogels, thereby tailoring their frictional properties. The method is based on oxygen inhibition of the free-radical polymerization reaction during synthesis and enables (i) control of friction over more than an order in magnitude and (ii) spatial control of friction as either a continuous gradient or a distinct pattern. The presented method has successfully been applied to acrylamide-, diacrylate- and methacrylate-based gels, illustrating the universality of the presented method, and its potential use in the above-mentioned applications.

Oxygen inhibition of free-radical polymerization is the dominant mechanism behind the "mold effect" on hydrogels.

Hydrogel surfaces are of great importance in numerous applications ranging from cell-growth studies and hydrogel-patch adhesion to catheter coatings and contact lenses. A common method to control the structure and mechanical/tribological properties of hydrogel surfaces is by synthesizing them in various mold materials, whose influence has been widely ascribed to their hydrophobicity. In this work, we examine possible mechanisms for this "mold effect" on the surface of hydrogels during polymerization. Our results for polyacrylamide gels clearly rule out the effect of mold hydrophobicity as well as any thermal-gradient effects during synthesis. We show unequivocally that oxygen diffuses out of certain molding materials and into the reaction mixture, thereby inhibiting free-radical polymerization in the vicinity of the molding interface. Removal of oxygen from the system results in homogeneously cross-linked hydrogel surfaces, irrespective of the substrate material used. Moreover, by varying the amount of oxygen at the surface of the polymerizing solutions using a permeable membrane we are able to tailor the surface structures and mechanical properties of PAAm, PEGDA and HEMA hydrogels in a controlled manner.

Versatile Surface Modification of Hydrogels by Surface-Initiated, Cu0-Mediated Controlled Radical Polymerization.

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.

Linking Friction and Surface Properties of Hydrogels Molded Against Materials of Different Surface Energies.

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.

Creating an Interface: Rendering a Double-Network Hydrogel Lubricious via Spontaneous Delamination.

Hydrogels engineered with specific surface chemistries and architectures have found myriad applications in electronics, biofouling, biolubrication, and biomedical devices. Free-radical polymerization is frequently employed to construct covalently bonded networks in hydrogels, and any inhibition of the radical reactions by oxygen at the surface of the reaction mixture is generally undesirable. The internal stress caused by the resulting gradient in the cross-linking density during polymerization can give rise to a physical deformation of the surface, resulting in wrinkles, creases, or cracks. However, this oxygen-inhibition effect can be positively utilized to create finely controlled surface structures. We describe a two-step cross-linking strategy for the fabrication of a P(AAm-AMPS)/alginate double-network hydrogel in the presence of air, which enables greater independent control over surface chemistry and functionality than homogeneously processed conventional double-network hydrogels. An alginate-rich "skin" layer is spontaneously delaminated due to the mechanical instability and osmotic mismatch between the swollen double-network hydrogel matrix and the rigid "skin" layer. Removal of the "skin" layer results in a lubricious surface with coefficients of friction as low as 0.02 against glass in aqueous solutions. The proposed strategy can be generalized to develop soft functional materials with unique structures and properties and precise control over the surface chemistry.

Hairy and Slippery Polyoxazoline-Based Copolymers on Model and Cartilage Surfaces.

Comb-like polymers presenting a hydroxybenzaldehyde (HBA)-functionalized poly(glutamic acid) (PGA) backbone and poly(2-methyl-2-oxazoline) (PMOXA) side chains chemisorb on aminolized substrates, including cartilage surfaces, forming layers that reduce protein contamination and provide lubrication. The structure, physicochemical, biopassive, and tribological properties of PGA-PMOXA-HBA films are finely determined by the copolymer architecture, its reactivity toward the surface, i.e. PMOXA side-chain crowding and HBA density, and by the copolymer solution concentration during assembly. Highly reactive species with low PMOXA content form inhomogeneous layers due to the limited possibility of surface rearrangements by strongly anchored copolymers, just partially protecting the functionalized surface from protein contamination and providing a relatively weak lubrication on cartilage. Biopassivity and lubrication can be improved by increasing copolymer concentration during assembly, leading to a progressive saturation of surface defects across the films. In a different way, less reactive copolymers presenting high PMOXA side-chain densities form uniform, biopassive, and lubricious films, both on model aminolized silicon oxide surfaces, as well as on cartilage substrates. When assembled at low concentrations these copolymers adopt a "lying down" conformation, i.e. adhering via their backbones onto the substrates, while at high concentrations they undergo a conformational transition, assuming a more densely packed, "standing up" structure, where they stretch perpendicularly from the substrate. This specific arrangement reduces protein contamination and improves lubrication both on model as well as on cartilage surfaces.

Modeling soft, permeable matter with the proper generalized decomposition (PGD) approach, and verification by means of nanoindentation.

Understanding sliding and load-bearing mechanisms of biphasic soft matter is crucial for designing synthetic replacements of cartilage, contact-lens materials or coatings for medical instruments. Interstitial fluid pressurization is believed to be the intrinsic load-carrying phenomenon governing the frictional properties. In this study, we have characterized permeability and identified the fluid contribution to the support of load during Atomic Force Microscopy (AFM) nanoindentation of soft polymer brushes in aqueous environments, by means of the Proper Generalized Decomposition (PGD) approach. First, rate-dependent AFM nanoindentation was performed on a poly(acrylamide) (PAAm) brush in an aqueous environment, to probe the purely elastic as well as poro-viscoelastic properties. Second, a biphasic model decoupling the fluid and solid load contributions was proposed, using Darcy's equation for liquid flow in porous media. Using realistic time-dependent simulations requires many direct solutions of the 3D partial differential equation, making modeling very time-consuming. To efficiently alleviate the time-consumption of multi-dimensional modeling, we used PGD to solve a Darcy model defined in a 7D domain, considering all the unknowns and material properties as extra coordinates of the problem. The obtained 7D simulation results were compared to the experimental results by using a direct Newton algorithm, since all sensitivities with respect to the model parameters are readily available. Thus, a simulation-based solution for depth- and rate-dependent permeability can be obtained. From the PGD-based model permeability is calculated, and the velocity- and pressure-fields in the material can be obtained in real-time in 3D by adjusting the parameters to the experimental values. The result is a step forward in understanding the fluid flow, permeability and fluid contributions to the load support of biphasic soft matter.

ATR-IR Investigation of Solvent Interactions with Surface-Bound Polymers.

Solvent interactions with bulk and surface-bound polymer brushes are crucial for functionalities such as controlled friction and thermoresponsive adhesion. To study such interactions, the temperature-induced solvent-quality changes and the effect of surface tethering on the mechanical and tribological properties of poly(dodecyl methacrylate) (P12MA) brushes have been investigated by means of attenuated total reflection infrared spectroscopy (ATR-IR), as well as atomic force microscopy (AFM) and lateral force microscopy (LFM). These results have been compared with temperature-dependent UV-visible spectrophotometry (UV-vis) data for the corresponding bulk polymer solutions. The ATR-IR results clearly show that increasing temperature enhances ethanol uptake in P12MA, which results in film swelling. This is accompanied by a marked increase in both adhesion and friction. We have also shown that a combination of solvents, such as toluene and ethanol, can lead to a temperature-dependent solvent partitioning within the polymer brush. To our knowledge this is the first time preferential solvent uptake in a grafted-from brush has been monitored via in situ ATR-IR. Moreover, we have observed remarkably different behavior for polymer chains in solution compared to the behavior of similar chains bound to a surface. The presented findings on the temperature-dependent solvent interactions of surface-grafted P12MA reveal previously unknown solvation phenomena and open up a range of possible applications in the area of stimuli-responsive materials.