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    Rejuvenation through plastic deformation of a La-based metallic glass measured by fast-scanning calorimetry
    (Amsterdam : Elsevier B.V., 2020) Meylan, C.M.; Orava, J.; Greer, A.L.
    We explore the glassy states achievable after a metallic glass is formed on liquid quenching. Samples of La55Al25Ni20 (at.%) metallic glass (rod and ribbon) are studied. The extent of structural relaxation at room temperature is characterized for this low-glass-transition temperature glass. Plastic deformation (uniaxial compression) rejuvenates the glass to states of higher enthalpy characteristic of glass formation at high cooling rate. Deformation increases the heterogeneity of the glass, widening the spectrum of relaxation times. The extent of rejuvenation in samples of low aspect ratio is compared with that under conditions of high constraint in notched samples. The deformation-induced rejuvenation is particularly susceptible to reduction on subsequent ageing. Fast-scanning calorimetry is useful in characterizing the dynamics of structural relaxation. The shadow glass transition is more evident on fast heating, and is observed in this glass for the first time. A new excess exothermic effect is observed before the glass transition.
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    Pentacene in 1,3,5-Tri(1-naphtyl)benzene: A Novel Standard for Transient EPR Spectroscopy at Room Temperature
    (Wien [u.a.] : Springer, 2021) Schröder, Mirjam; Rauber, Daniel; Matt, Clemens; Kay, Christopher W. M.
    Testing and calibrating an experimental setup with standard samples is an essential aspect of scientific research. Single crystals of pentacene in p-terphenyl are widely used for this purpose in transient electron paramagnetic resonance (EPR) spectroscopy. However, this sample is not without downsides: the crystals need to be grown and the EPR transitions only appear at particular orientations of the crystal with respect to the external magnetic field. An alternative host for pentacene is the glass-forming 1,3,5-tri(1-naphtyl)benzene (TNB). Due to the high glass transition point of TNB, an amorphous glass containing randomly oriented pentacene molecules is obtained at room temperature. Here we demonstrate that pentacene dissolved in TNB gives a typical “powder-like” transient EPR spectrum of the triplet state following pulsed laser excitation. From the two-dimensional data set, it is straightforward to obtain the zero-field splitting parameters and relative populations by spectral simulation as well as the B1 field in the microwave resonator. Due to the simplicity of preparation, handling and stability, this system is ideal for adjusting the laser beam with respect to the microwave resonator and for introducing students to transient EPR spectroscopy. © 2021, The Author(s).
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    Glassy dynamics of poly(2-vinyl-pyridine) brushes with varying grafting density
    (London : Royal Soc. of Chemistry, 2015) Neubauer, Nils; Winkler, René; Tress, Martin; Uhlmann, Petra; Reiche, Martin; Kipnusu, Wycliffe Kiprop; Kremer, Friedrich
    The molecular dynamics of poly(2-vinyl-pyridine) (P2VP) brushes is measured by Broadband Dielectric Spectroscopy (BDS) in a wide temperature (250 K to 440 K) and broad spectral (0.1 Hz to 1 MHz) range. This is realized using nanostructured, highly conductive silicon electrodes being separated by silica spacers as small as 35 nm. A “grafting-to”-method is applied to prepare the P2VP-brushes with five different grafting densities (0.030 nm−2 to 0.117 nm−2), covering the “true-brush” regime with highly stretched coils and the “mushroom-to-brush” transition regime. The film thickness ranges between 1.8 to 7.1 (±0.2) nm. Two relaxations are observed, an Arrhenius-like process being attributed to fluctuations in the poly(glycidyl-methacrylate) (PGMA) linker used for the grafting reaction and the segmental dynamics (dynamic glass transition) of the P2VP brushes. The latter is characterized by a Vogel–Fulcher–Tammann dependence similar to bulk P2VP. The results can be comprehended considering the length scale on which the dynamic glass transition (≤1 nm) takes place.