Hydrogels are soft hydrated polymer networks that are widely used in research and industry due to their favorable properties and similarity to biological tissues. However, it has long been difficult to create a hydrogel emulating the heterogeneous structure of special tissues, such as cartilage. One potential avenue to develop a structural variation in a hydrogel is the “mold effect,” which has only recently been discovered to be caused by absorbed oxygen within the mold surface interfering with the polymerization. This induces a dilute gradient-density surface layer with altered properties. However, the precise structure of the gradient-surface layer and its contact response have not yet been characterized. Such knowledge would prove useful for designs of composite hydrogels with altered surface characteristics. To fully characterize the hydrogel gradient-surface layer, we created five hydrogel compositions of varying monomer and cross-linker content to encompass variations in the layer. Then, we used particle exclusion microscopy during indentation and creep experiments to probe the contact response of the gradient layer of each composition. These experiments showed that the dilute structure of the gradient layer follows evolving contact behavior allowing poroelastic squeeze-out at miniscule pressures. Stiffer compositions had thinner gradient layers. This knowledge can potentially be used to create hydrogels with a stiff load-bearing bulk with altered surface characteristics tailored for specific tribological applications.

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