The molecular mobility of amorphous ibuprofen has been investigated by broadband dielectric relaxation spectroscopy (DRS) covering a temperature range of more than 200 K. Four different relaxation processes, labeled as alpha, beta, gamma, and D, were detected and characterized, and a complete relaxation map was given for the first time. The gamma-process has activation energy E a = 31 kJ.mol (-1), typical for local mobility. The weak beta-relaxation, observed in the glassy state as well as in the supercooled state was identified as the genuine Johari-Goldstein process. The temperature dependence of the relaxation time of the alpha-process (dynamic glass transition) does not obey a single VFTH law. Instead two VFTH regimes are observed separated by a crossover temperature, T B = 265 K. From the low temperature VFTH regime, a T g (diel) (tau =100 s) = 226 K was estimated, and a fragility or steepness index m = 93, was calculated showing that ibuprofen is a fragile glass former. The D-process has a Debye-like relaxation function but the temperature dependence of relaxation time also follows the VFTH behavior, with a Vogel temperature and a pre-exponential factor which seem to indicate that its dynamics is governed by the alpha-process. It has similar features as the Debye-type process observed in a variety of associating liquids, related to hydrogen bonding dynamics. The strong tendency of ibuprofen to form hydrogen bonded aggregates such as dimers and trimers either cyclic or linear which seems to control in particular the molecular mobility of ibuprofen was confirmed by IR spectroscopy, electrospray ionization mass spectrometry, and MD simulations.

To study the influence of PEO on the relaxation process of PMMA, the real and imaginary parts of the permittivity, ′ and ′′, of PEO/PMMA blends (with PEO contents up to 25 wt %) were measured as a function of frequency and temperature, and the results obtained were compared with those of pure PMMA. It is shown that the presence of PEO broadens the relaxation process of PMMA and increases its relaxation strength. The lower T g component (PEO) has a plasticizing effect on the relaxation of PMMA, for the blends with 10 and 15% PEO. The splitting of the Rβ process of PMMA seems to be affected by the presence of the second component, being the onset of the R relaxation shifted to lower temperatures with the increase of PEO concentration. The DSC thermograms show a single glass transition temperature, which is displaced to lower temperatures with the increase of PEO content, and no evidence of crystallinity was found. The presence of a singular broad transition in the 20% PEO blend, evidenced in both dielectric and calorimetric experiments, may be associated with the merging of the R and β process and to concentration fluctuations, confirming that this blend lies in the border of the miscibility/immiscibility region.