Bram Vanroy

Glassy dynamics of soft matter under 1D confinement: How irreversible adsorption affects molecular packing, mobility gradients and orientational polarization in thin films

The structural dynamics of polymers and simple liquids confined at the nanometer scale has been intensively investigated in the last two decades in order to test the validity of theories on the glass transition predicting a characteristic length scale of a few nanometers. Although this goal has not yet been reached, the anomalous behavior displayed by some systems --e.g. thin films of polystyrene exhibit reductions of Tg exceeding 70K and a tremendous increase in the elastic modulus-- has attracted a broad community of researchers, and provided astonishing advancement of both theoretical and experimental soft matter physics. 1D confinement is achieved in thin films, which are commonly treated as systems at thermodynamic equilibrium where free surfaces and solid interfaces introduce monotonous mobility gradients, extending for several molecular sizes. Limiting the discussion to finite-size and interfacial effects implies that film thickness and surface interactions should be sufficient to univocally determine the deviation from bulk behavior. On the contrary, such an oversimplified picture, although intuitive, cannot explain phenomena like the enhancement of segmental mobility in proximity of an adsorbing interface, or the presence of long-lasting metastable states in the liquid state. Based on our recent work, we propose a new picture on the dynamics of soft matter confined in ultrathin films, focusing on non-equilibrium and on the impact of irreversibly chain adsorption on the structural relaxation. We describe the enhancement of dynamics in terms of the excess in interfacial free volume, originating from packing frustration in the adsorbed layer (Guiselin brush) at t* ≪ 1 , where t* is the ratio between the annealing time and the time scale of adsorption. Prolonged annealing at times exceeding the reptation time (usually t* ≫ 1 induces densification, and thus reduces the deviation from bulk behavior. In this Colloquium, after reviewing the experimental approaches permitting to investigate the structural relaxation of films with one, two or no free surfaces by means of dielectric spectroscopy, we propose several methods to determine gradients of mobility in thin films, and then discuss on the unexploited potential of analyses based on the time, temperature and thickness dependence of the orientational polarization via the dielectric strength.Graphical abstract

1,2,4-Triazolium perfluorobutanesulfonate as an archetypal pure protic organic ionic plastic crystal electrolyte for all-solid-state fuel cells

1,2,4-Triazolium perfluorobutanesulfonate (1), a novel, pure protic organic ionic plastic crystal (POIPC) with a wide plastic crystalline phase, has been explored as a proof-of-principle anhydrous proton conductor for all-solid-state high temperature hydrogen/air fuel cells. Its physicochemical properties, including thermal, mechanical, structural, morphological, crystallographic, spectral, and ion-conducting properties, as well as fuel cell performances, have been studied comprehensively in both fundamental and device-oriented aspects. With superior thermal stability, 1 exhibits crystal (phase III), plastic crystalline (phase II and I) and melt phases successively from −173 °C to 200 °C. Differential scanning calorimetry and temperature-dependent powder X-ray diffraction (XRD) measurements together with polarized optical microscopy and thermomechanical analysis reveal the two solid–solid phase transitions of 1 at 76.8 °C and 87.2 °C prior to the melting transition at 180.9 °C, showing a wide plastic phase (87–181 °C). Scanning electron microscopy displays the morphology of different phases, indicating the plasticity in phase I. Single-crystal XRD studies reveal the molecular structure of 1 and its three-dimensional N–H⋯O hydrogen bonding network. The influence of the three-dimensional hydrogen bonding network on the physicochemical properties of 1 has been highlighted. The temperature dependence of hydrogen bonding is investigated by variable-temperature infrared spectroscopy. The sudden weakening of hydrogen bonds at 82 °C seems to be coupled with the onset of orientational or rotational disorder of the ions. The temperature dependence of ionic conductivity in the solid and molten states is measured via impedance spectroscopy and current interruption technique, respectively. The Arrhenius plot of the ionic conductivity assumes a lower plateau region (phase I, 100–155 °C) with a low activation energy of ∼36.7 kJ mol−1 (i.e. ∼0.38 eV), suggesting likely a Grotthuss mechanism for the proton conduction. Variable-temperature infrared analysis, optical morphological observations, and powder XRD patterns further illustrate the structural changes. Electrochemical hydrogen pumping tests confirm the protonic nature of the ionic conduction observed in the lower plateau region. Finally, measurements of the open circuit voltages (OCVs) and the polarization curves of a dry hydrogen/air fuel cell prove the long-range proton conduction. At 150 °C, a high OCV of 1.05 V is achieved, approaching the theoretical maximum (1.11 V).