Surface Forces Characterization of Concentrated PMMA Brush Layers under Applied Load and Shear

Concentrated polymer brushes (CPBs) are known to exhibit excellent lubrication properties. However, the frictional behaviors of CPBs vary, depending on their preparation and operating conditions. In order to understand such complicated properties, it is necessary to determine their structures and correlate them with their properties, during shear motion. In this study, we employed surface forces and resonance shear measurement (RSM) as well as refractive index measurement using fringes of equal chromatic order (FECO) for studying the structure of the CPBs of poly(methyl methacrylate) (PMMA) in toluene. The obtained elastic (k_s) and viscous (b_s) parameters based on the RSM for the PMMA-PMMA were higher than those obtained for PMMA-silica over the entire distance range. With the increasing shear amplitude on the PMMA-PMMA under an applied load, the b_s value first increased and then decreased while the k_s value monotonically decreased. These behaviors were consistent with those of the thicker CPBs reported in a previous paper (Soft Matter, 2019). Thus, the dynamics of the CPBs under the applied load and shear were not dependent on the thickness of the polymer brushes in this case. The density distribution of the swollen PMMA brushes along the distance in the thickness direction of the brush layer was estimated by using the measured refractive index values, showing that the fraction of the PMMA brushes in the outer region from the surface (20% in the thickness) was ca. 10%. This lower density region near the surface of the swollen CPBs enabled them to interpenetrate with each other. Changes in the refractive index value under shear were observed, indicating that the interpenetrated PMMA chains were pulled out with increasing shear amplitude. These results demonstrated that broader applications of CPBs are possible by regulating the friction between them under different operating conditions, even for usually lubricious CPBs.