Plasticization by PEG as a Strategy to Tune Surface Properties of Hypromellose Films at the Nano/Macroscale

Cellulose ether, like hypromellose (HM), is an extremely versatile material that is widely used in pharmaceutical products as film coatings. To modify the surface properties of HM films, additives are routinely included during the film formulation process, which are typically hydrophobic lubricants or hydrophilic plasticizers. Plasticizers increase the flexibility and reduce the brittleness of the film. The first goal of this study is to demonstrate that plasticization of HM films by low-molecular-weight (400 g∙mol−1) polyethylene glycol (PEG) allows tuning adhesion and friction properties of HM films, both at nano- and macroscales. Surface morphology, surface energy, nano/macro adhesion, and nano/macro friction coefficient were studied by atomic force microscopy (AFM) in adhesion or friction modes at the nanoscale, wettability, and probe-tack adhesion, as well as pin-on-disk friction experiments at the macroscale. The results show that the addition of PEG decreases the Young’s modulus and the Tg of HM-plasticized films while increasing their strain at break and surface energy. The macroadhesion force increases from 9 to 90 mN by the addition of 40% w/w of PEG, whereas the macrofriction coefficient is reduced by 50%. The hypothesis of insertion of plasticizer molecules in HM chains’ nano-domains is evidenced and explains these results. The second goal of this study is to investigate nanoscale versus macroscale correlation of adhesion and friction properties and the role of adhesion in friction experiments. The results show, first, that the evolution of the adhesion energy at the macroscale as a function of adhesion energy at the nanoscale is linear. On the contrary, a high friction coefficient at the nanoscale corresponds to a low friction coefficient at the macroscale and vice versa, showing a first linear decrease for PEG contents ranging from 0 to 30% (w/w) and the second linear decrease, less pronounced, is observed for PEG contents ranging from 30 to 40% (w/w). The hypothesis of a difference in contact pressure applied on the probe at both scales, as well as HM-PEG surface phase separation at a high PEG content (>30% w/w), is proposed to explain this difference. The variations in friction coefficients are linear according to the PEG plasticizer content and suggest its lubricant role in HM-Plasticized films. Finally, the interplay between adhesion and friction, in friction experiments, is evidenced and appears dominant at the nanoscale.