Size-Controllable and pH-Sensitive Whey Protein Microgels as High-Performance Aqueous Biolubricants

Developing efficient aqueous biolubricants has become a significant focus of research due to their prevalence in biotribological contacts and enormous potential in soft matter applications. In this study, size-controllable, pH-sensitive whey protein microgels were prepared using a water-in-water emulsion template method from protein-polysaccharide phase separation. The granular hydrogel from the protein microgels exhibited superior lubricity, obtaining 2.7-fold and 1.7-fold reductions in coefficient of friction (μ) compared to native protein and human saliva (μ = 0.30 compared to 0.81 and 0.52, respectively). The microgels also exhibited outstanding load-bearing capabilities, sustaining lubrication under normal forces up to 5 N. Microgels with a smaller size (1 μm) demonstrated better lubricating performance than 6 and 20 μm microgels. The exceptional lubricity was from a synergistic effect of the ball-bearing mechanism and the hydration state of the microgels. Particularly at pH 7.4, the hydration layer surrounding highly negative charges contributed to the electrostatic repulsion among the swollen microgels, leading to an improved buffer ability to separate contact surfaces and effective rolling behavior. Such pH-dependent repulsion was evidenced using a surface forces apparatus that the adhesion between the whey protein-coated surfaces and protein-mica surfaces decreased from 4.49 to 0.97 mN/m and from 7.89 to 0.36 mN/m, respectively, with pH increasing from the isoelectronic point to 7.4. Our findings fundamentally elucidated the tribo-rheological properties and lubrication mechanisms of the whey protein microgels with excellent biocompatibility and environmental responsiveness, offering novel insights for their food and biomedical applications requiring aqueous biolubrication.