A polymer model exhibiting heterogeneous Johari–Goldstein (JG) secondary relaxation is studied by extensive molecular-dynamics simulations of states with different temperature and pressure. Time–temperature–pressure superposition of the primary (segmental) relaxation is evidenced. The time scales of the primary and the JG relaxations are found to be highly correlated according to a power law. The finding agrees with key predictions of the Coupling Model (CM) accounting for the decay in a correlation function due to the relaxation and diffusion of interacting systems. Nonetheless, the exponent of the power law, even if it is found in the range predicted by CM (0<ξ<1), deviates from the expected one. It is suggested that the deviation could depend on the particular relaxation process involved in the correlation function and the heterogeneity of the JG process.

The vibrational dynamics of a model polymer glass is studied by Molecular Dynamics simulations. The focus is on the “soft” monomers with high participation to the lower-frequency vibrational modes contributing to the thermodynamic anomalies of glasses. To better evidence their role, the threshold to qualify monomers as soft is made severe, allowing for the use of systems with limited size. A marked tendency of soft monomers to form quasi-local clusters involving up to 15 monomers is evidenced. Each chain contributes to a cluster up to about three monomers and a single cluster involves a monomer belonging to about 2–3 chains. Clusters with monomers belonging to a single chain are rare. The open and tenuous character of the clusters is revealed by their fractal dimension df<2. The inertia tensor of the soft clusters evidences their strong anisotropy in shape and remarkable linear correlation of the two largest eigenvalues. Owing to the limited size of the system, finite-size effects, as well as dependence of the results on the adopted polymer length, cannot be ruled out.

We review past and recent work carried out on viscous liquids, amorphous and semicrystalline polymers by multifrequency high-field electron paramagnetic resonance (HF-EPR) facility in Pisa. The emphasis is on the enhanced ability to provide fine details of the reorientation process of the paramagnetic guest, the spin probe, revealing features driving the dynamics of the host system, including the energy-barrier distribution of glassy polymers, the dynamical heterogeneity of semicrystalline polymers, and the dynamical changes occurring at the critical temperature predicted by the ideal mode-coupling theory.

For the first time in this study, the utilization of rice bran oil (RBO) as possible totally eco-friendly plasticizer for poly(lactic acid) (PLA) has been investigated. For comparison, the behavior of soybean oil (SO) has also been analyzed. Both oils are not completely miscible with PLA. However, certain compatibility exists between PLA and (i) RBO and (ii) SO, because demixing is not complete. Although not totally miscible, RBO and SO are able to reduce the viscosity of the PLA+RBO and PLA+SO mixtures, which attests that a small amount of RBO or SO can be successfully added to PLA to improve its processability. Additionally, the mechanical properties of the PLA+RBO and PLA+SO mixtures exhibit trends typical of plasticizer-polymer systems. More interestingly, RBO was found to accelerate the growth of PLA α’-crystals at a low crystallization temperature. This feature is appealing, because the α’-phase presents lower elastic modulus and higher permeability to water vapor in comparison to the α-phase, which grows at high temperatures. Thus, this study demonstrates that the addition of RBO to PLA in small percentages is a useful solution for a faster preparation of PLA materials containing mainly the α’-phase.

The thermal, mechanical and viscoelastic properties of biocomposites of poly(lactic acid) (PLA) with 20 wt.% of potato pulp powder were investigated. The potato pulp powder utilized is a byproduct from the production and extraction of starch. The results showed that the potato pulp powder does not act as reinforcement, but as filler for PLA, due to an unfavorable aspect ratio and the irregular shape of the particles. In order to improve the mechanical response of the PLA/potato pulp powder biocomposites, surface treatment of the potato pulp particles with bio-based and petroleum-based waxes was investigated. This treatment was found to improve the properties of the biocomposites, enhancing the adhesion between the PLA based polymeric matrix and the potato pulp fibers. The best result is obtained with a petroleum-based wax, but also the bio-based waxes lead to good mechanical properties of the biocomposite. Thus, the addition to PLA of potato pulp powder, treated with waxes, appears a method able to (i) utilize and valorize an abundant agro-food biomass such as potato pulp, according to the principles of circular economy, (ii) favor the production of articles with properties valuable for practical applications, and (iii) reduce the cost of the final products, considering the relatively high cost of PLA.

Glass-forming systems approaching their glass transition exhibit universal correlations between picosecond vibrational dynamics and long-time structural relaxation, which can be described by the same master curve in the bulk or confined conditions. In this work, we study at a fundamental level the effects of the reduction of spatial dimensionality on this phenomenon. We perform molecular dynamics simulations of a metallic glass-formers in two dimensions (2D). We show that in the supercooled regime particle localization in the cage and structural relaxation are blurred by long-wavelength fluctuations specific to low-dimensional systems. Once these effects are properly removed, we demonstrate that the fast dynamics and slow relaxation comply, without any adjustment, with same scaling between the structural relaxation time and the Debye?Waller factor, originally observed in three-dimensions (3D).

The thermal, mechanical, and rheological properties of biocomposites of poly(lactic acid) (PLA) with potato pulp powder were investigated in order to (1) quantify how the addition of this filler modifies the structure of the polymeric material and (2) to obtain information on the possible miscibility and compatibility between PLA and the potato pulp. The potato pulp powder utilized is a residue of the processing for the production and extraction of starch. The study was conducted by analyzing the effect of the potato pulp concentration on the thermal, mechanical, and rheological properties of the biocomposites. The results showed that the potato pulp powder does not act as reinforcement but as filler for the PLA polymeric matrix. A progressive decrease in elastic modulus, tensile strength, and elongation at break was observed with increasing the potato pulp percentage. This moderate loss of mechanical properties, however, still meets the technical requirements indicated for the production of rigid packaging items. The incorporation of potato pulp powder to PLA offers the possibility to reduce the cost of the final products and promotes a circular economy approach for the valorization of agro-food waste biomass.

The reorientation of the guest 4-methoxy-TEMPO (spin probe) in the disordered fraction of semicrystalline poly(dimethylsiloxane) (PDMS) is investigated by high-field electron paramagnetic resonance (HF-EPR) at 190 and 285 GHz. Accurate numerical simulations of the HF-EPR lineshapes evidence that the reorientation times of the spin probes are distributed between the melting temperature T-m and T-m-30 K. The distribution exhibits, in addition to a broad component, a narrow component with low mobility up to the PDMS melting point. It is shown that the temperature dependence of the reorientation time of the spin probes with low mobility is the same of the spin probes in glassy PDMS. The result suggests that the low-mobility fraction is localized in the so-called rigid amorphous fraction.

The reorientation of the paramagnetic guest 4-methoxy-TEMPO (spin probe) in the disordered fraction of semicrystalline poly(dimethylsiloxane) (PDMS) is investigated by high-field electron paramagnetic resonance (HF-EPR) at 190 and 285 GHz. The distribution of reorientation times is evidenced by accurate numerical simulations of the HF-EPR line shapes above 200 K. The distribution exhibits a bimodal structure with (i) a broad component corresponding to spin probes with fast and intermediate mobility located in the disordered fraction far from the crystallites and (ii) a narrow component corresponding to spin probes with extremely low mobility trapped close to the crystallites in a glassy environment persisting up to the PDMS melting. The spin probe undergoes an exchange process between the trapped and the more mobile fractions which is accounted for by an equilibrium reversible process with standard Gibbs free energy of reaction per spin probe mole Delta G(r)(0) similar or equal to 4(Delta H-m - T Delta S-m), where Delta S-m is the equilibrium melting entropy per monomer mole following the absorption of the heat Delta H-m. The process is interpreted as signature of reversible tertiary nucleation, occurring at the intersection of crystalline surfaces, thus suggesting surface roughness of the crystalamorphous interface. It becomes thermodynamically favored at temperatures higher than T similar to 209 K where the onset of PDMS melting is located according to differential scanning calorimetry.

The reorientation of TEMPO spin probe in semicrystalline poly(dimethylsiloxane) (PDMS) is investigated in the temperature range from the glassy region (below 147 K) up to the melt (above about 230 K) by high-field electron paramagnetic resonance (HF-EPR) spectroscopy at two different Larmor frequencies (190 and 285 GHz). The spin probe is confined in the disordered phase. Accurate numerical simulations evidence that the spin probe undergoes activated jump reorientation overcoming an exponential distribution of barrier heights characteristic of highly constrained systems and resulting in a power-law distribution of the reorientation times. Below 180 K the spin probe is coupled to local relaxations and does not sense the glass transition. A strong narrowing of the distribution of the reorientation times and a sudden drop of the mean value are observed at similar or equal to 213 K, above the onset of the melting at similar or equal to 209 K. Strikingly, it is found that the faster fraction of the spin probes does not sense the melting and couples to the segmental motion of the bulk amorphous PDMS from about 200 K onward. Our findings support the conclusion that the faster and the slower TEMPO molecules are located in (or very close to) the mobile (MAP) and the rigid (RAF) amorphous fractions of PDMS, respectively. The results suggest that MAP is negligible close to the glass transition but it is present above about 200 K, whereas RAF at about 211 K is reduced to about 896 and softens above 213 K, well below the melting transition (similar or equal to 230 K). Similarities between the disordered phase of semicrystalline PDMS and the PDMS layers in poly(styrene) PDMS diblock are discussed.

The cold crystallization at the air interface in fairly thick films of poly( ethylene terephthalate) (PET) was studied by combining attenuated total reflectance (ATR) infrared spectroscopy and X-ray diffraction (XRD) analysis methods. In ATR analysis, Ge and ZnSe were both used as internal reflectance elements to gain information at two different penetration depths from the air interface of the films. Samples were crystallized for different time at the selected temperature so to obtain kinetics plots of the crystallization process. The kinetics obtained by X-ray and ATR analysis on Ge and ZnSe clearly indicate that the crystallization at the film surface is faster than that in the bulk.All kinetics plots were analyzed with Avrami and Malkin macrokinetics models. Finally a method based on the deconvolution of the surface contribution from the bulk was developed to deeply investigate the difference between the crystallization at the air interface and in the bulk. The method is based on the use of two Malkin equations, one describing the behavior at the surface and the other in the bulk. It has allowed to roughly estimate the thickness of the surface layer, which was found to be in the submicrometer range. Finally, the Malkin parameters obtained in the analysis clearly indicated that the crystallization rate at the surface is faster because of the higher nucleation rate in this region than in the bulk. (C) 2014 Elsevier Ltd. All rights reserved.

The reorientation of a small paramagnetic tracer in poly(dimethylsiloxane) (PDMS) has been investigated by high-field electron paramagnetic resonance spectroscopy at a Larmor frequency of 285 GHz. The tracer is confined in the disordered phase of the semicrystalline PDMS. A sudden change of the rotational dynamics is observed close to the melting point (213 K) of the crystallites. This points to strong coupling between the crystalline and the disordered fractions of PDMS. Below the glass transition (\(T_\mathrm{g} \sim 150 \mathrm{K}\)), the tracer reorientation occurs via small angle jumps, with no apparent distribution of the correlation times. Above \(T_\mathrm{g}\), a power-law distribution of correlation times is evidenced.

Abstract High-field high-frequency Electron Paramagnetic Resonance spectroscopy (HF 2 -EPR) is a powerful tool to investigate, with ultra-high angular resolution, the rotational dynamics of complex systems like polymers, viscous fluids and glasses. Usually, information is drawn by detailed numerical analysis of the overall lineshape. Here, we present a simplified analytical model of the line shifts due to the rotational dynamics of the paramagnetic centre. The model captures the basic features of the reorientation process (time scale and size of the angular jump). It is compared with experimental results concerning the reorientation of a paramagnetic guest molecule dissolved in polystyrene. We find that, if the rotational model to describe the reorientation of the radical is consistent, the best-fit parameters yield equally acceptable best-fits of the overall spectrum by numerical simulations and dynamical line shifts by independent analytic expressions.

The EPR spectrum of Mn2+ in microcrystalline calcite geomaterials (e.g., marbles, travertines) possesses exceptional diagnostic characteristics, allowing to relate samples to their origin (natural/synthetic, inorganic, organogenic,...) and to evaluate the details of impurities clustering. This information, beyond their mineralogical and geochemical interest, is of paramount importance for environmental, palaeoclimatic, and cultural heritage studies.Accessing the information hidden in the Mn2+ EPR spectrum relies on disentangling spurious self-correlation among spin Hamiltonian parameters in the powder spectrum. In the present study, this goal is achieved through a systematic comparison of the temperature dependencies of four different microcrystalline calcite geomaterials. Accordingly, an assessment of the internal correlation structure of the spin Hamiltonian parameters is provided and the most sensitive discriminating parameters, which are able to mark samples, are identified.It has been found that the spin Hamiltonian parameters useful for discrimination purposes are those which are dependent on the ligand field interaction, whereas the Fermi contact interaction, as well as the spin-spin, spin-phonon, and spin-lattice interactions, are not able to "store" information related to formation processes, nor post-depositional events. This characteristic behavior is ascribed to the occurrence of mosaic structure and to the clustering among Mn2+ and other impurity ions, which are able to induce a strong and variable ligand field interaction.In particular, the proposed method appears fully able to reveal the biogenic origin of microcrystalline calcites and to trace post-depositional events.

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu3SnS4, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu3SnS4 crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)(2)Cu(II)SnS4 and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.

The reorientation of one paramagnetic molecule in glassy polystyrene is studied by high-field electron paramagnetic resonance spectroscopy at four different Larmor frequencies between 9.5 and 285 GHz. On increasing the Larmor frequency, the lineshape exhibits larger sensitivity to the rotational motion of the radical. Unfreezing the rotational dynamics by increasing the reorientation rate leads to considerable line shifts, whereas broadening effects are not dominant. The finding is evidence that the paramagnetic Molecule undergoes small-angle reorientation in the glassy matrix.

A multifrequency Electron Paramagnetic Resonance (EPR) investigation of Ce3+ impurities in PbWO4 single-crystals at the conventional microwave frequency (CMF) (X-band: 9.43GHz) and at the high frequencies/fields (HF) 95, 190 and 285GHz was carried out. The resulting spectra are well described at all frequencies by an axial spin-Hamiltonian corresponding to an effective spin one-half system in a tetragonal site symmetry. The diagonal values of the effective g matrix of the lowest doublet of the ground multiplet, g‖ and g⊥, are frequency dependent at high fields. For the magnetic field perpendicular to the tetragonal axis, the g⊥-parameter exhibits also a small azimuthal angular dependence, which is frequency dependent, corresponding to the tetragonal S4 symmetry. These HF effects are associated with the mixing by the large Zeeman interaction of some of the upper-lying doublets of the ground multiplet into the lowest-lying doublet states. The CMF and multifrequency HF-EPR analysis gives a good description of the magnetic properties and allows an estimation of the crystal field splitting of the ground multiplet of Ce3+ ions with tetragonal symmetry S4 in the PbWO4 scintillator.

A multifrequency electron paramagnetic resonance (EPR) investigation of Nd(3+) impurities in PbWO(4) single-crystals at the conventional microwave frequency (MF) 9.43 GHz, and at the 95, 190, and 285 GHz high frequencies was carried out. The resulting spectra are well described at all frequencies by an axial spin-Hamiltonian corresponding to an effective electron spin of one-half and to a tetragonal symmetry. For the magnetic field along the tetragonal axis, the g(parallel)-factor and the hyperfine constant A(parallel) of the lowest doublet of the ground multiplet decreases with frequency increase. For the magnetic field perpendicular to the tetragonal axis, the g(perpendicular)-factor exhibits a small azimuthal angular dependence that increases with increasing the frequency due to the S(4) site symmetry. The azimuthal angular dependence allows to clearly distinguish between different local axial symmetries. These properties are interpreted as high field/frequency (HF) effects associated with the mixing by the large Zeeman interaction of some of the upper-lying doublets of the ground multiplet into the lowest-lying doublet states. We show that from the combined analysis of the multifrequency MF- and HF-EPR spectra and of the optical data, an accurate description of the ground multiplet of the Kramers rare earth ions in solid matrices can be derived.