Predicting Dielectric and Shear-Rheology Properties of Glass-Forming Pharmaceutical Liquids from Each Other: Applications and Limitations.

Acetaminophen, nicotine, and lidocaine hydrochloride were investigated in their deeply supercooled liquid states using oscillatory shear rheology. The mechanical spectra of these drugs are presented in modulus, compliance, as well as fluidity formats. Their frequency profiles can be described via models adapted from the field of charge transport. Inspired by the success of this approach, the Barton-Nakajima-Namikawa relation, best known from the same field, was also tested. When adapted to rheology, this approach interrelates static and dynamic characteristics of viscous flow and was found to work excellently. The temperature dependence of the characteristic shear frequencies was checked against the shoving model, which relates them to the temperature-dependent instantaneous shear modulus and acceptable agreement was found. Combined with shear mechanical literature data on ibuprofen and indomethacin, a modified version of the phenomenological model by Gemant, DiMarzio, and Bishop (GDB) was employed to successfully predict the shape and amplitude of the dielectric spectra for all studied liquids, except for lidocaine hydrochloride. For the latter, the modified GDB model is suggested to aid in mapping out the reorientational part of the dielectric response, while the experimental results are strongly superimposed by ionic conduction phenomena. The reverse transformation, the calculation of rheological spectra based on dielectric ones, is also successfully demonstrated. For the example of acetyl salicylic acid, it is shown how dielectric spectra can be used to even predict rheological ones. The limits of the central parameter governing these mutual transformations, the electroviscoelastic material constant, and indications for its correlation with the dielectric relaxation strength are discussed. For pharmaceuticals characterized by a strong dynamical decoupling of the electrical from the mechanical degrees of freedom, the modified GDB model is not expected to be applicable.