Hierarchical Coherent Phonons in a Superatomic Semiconductor

The coupling of phonons to electrons and other phonons plays a defining role in material properties, such as charge and energy transport, light emission, and superconductivity. In atomic solids, phonons are delocalized over the 3D lattice, in contrast to molecular solids where localized vibrations dominate. Here, a hierarchical semiconductor that expands the phonon space by combining localized 0D modes with delocalized 2D and 3D modes is described. This material consists of superatomic building blocks (Re₆Se₈) covalently linked into 2D sheets that are stacked into a layered van der Waals lattice. Using transient reflectance spectroscopy, three types of coherent phonons are identified: localized 0D breathing modes of isolated superatom, 2D synchronized twisting of superatoms in layers, and 3D acoustic interlayer deformation. These phonons are coupled to the electronic degrees of freedom to varying extents. The presence of local phonon modes in an extended crystal opens the door to controlling material properties from hierarchical phonon engineering.     

Differential interference contrast x-ray microscopy with twin zone plates

X-ray imaging in differential interference contrast (DIC) with submicrometer optical resolution was performed by using a twin zone plate (TZP) setup generating focal spots closely spaced within the TZP spatial resolution of 160 nm. Optical path differences introduced by the sample are recorded by a CCD camera in a standard full-field imaging and by an aperture photodiode in a standard scanning transmission x-ray microscope. Applying this x-ray DIC technique, we demonstrate for both the full-field imaging and scanning x-ray microscope methods a drastic increase in image contrast (approximately 20x) for a low-absorbing specimen, similar to the Nomarski DIC method for visible-light microscopy.     

Engineering of poly(ε-caprolactone) microcarriers to modulate protein encapsulation capability and release kinetic

Drug delivery applications using biodegradable polymeric microspheres are becoming an important means of delivering therapeutic agents. The aim of this work was to modulate the microporosity of poly(ε-caprolactone) (PCL) microcarriers to control protein loading capability and release profile. PCL microparticles loaded with BSA (bovine serum albumin) have been de novo synthesized with double emulsion solvent evaporation technique transferred and adapted for different polymer concentrations (1.7 and 3% w/v) and stabilizer present in the inner aqueous phase (0.05, 0.5 and 1% w/v). SEM (scanning electron microscope) and CLSM (confocal laser scanning microscope) analysis map the drug distribution in homogeneously distributed cavities inside the microspheres with dimensions that can be modulated by varying double emulsion process parameters. The inner structure of BSA-loaded microspheres is greatly affected by the surfactant concentration in the internal aqueous phase, while a slight influence of polymer concentration in the oil phase was observed. The surfactant concentration mainly determines microspheres morphology, as well as drug release kinetics, as confirmed by our in-vitro BSA release study. Moreover, the entrapped protein remained unaltered during the protein encapsulation process, retaining its bio-activity and structure, as shown through a dedicated gel chromatographic analytical method.     

Charge transfer and partial pinning at the contacts as the origin of a double dip in the transfer characteristics of graphene-based field-effect transistors

We discuss the origin of an additional dip other than the charge neutrality point observed in the transfer characteristics of graphene-based field-effect transistors with a Si/SiO2 substrate used as the back-gate. The double dip is proved to arise from charge transfer between the graphene and the metal electrodes, while charge storage at the graphene/SiO2 interface can make it more evident. Considering a different Fermi energy from the neutrality point along the channel and partial charge pinning at the contacts, we propose a model which explains all the features observed in the gate voltage loops. We finally show that the double dip enhanced hysteresis in the transfer characteristics can be exploited to realize graphene-based memory devices.     

Experimental multiaxial fatigue tests realized with newly developed geometry specimens

In the literature there are many experimental results of multiaxial fatigue testing, usually generated by the combination of two or more cyclical loads. The cases in which samples are randomly stressed are rarer. Moreover, to generate particular stress states, the use of specific machinery for fatigue tests is usually required. For these reasons, the authors have created a particular geometry of specimens, which, when solicited by a single input of a random type, guarantees the creation of specific multiaxial stress states without using complex and costly instruments. The experimental tests were finally used for the validation of the multiaxial reduction method developed and currently utilized in the authors' design phase, though potentially used to verify all the other methodologies present in the literature.     

A model combining structure and properties of a 160/220 bituminous binder modified with polymer/clay nanocomposites. A rheological and morphological study

The present contribution focuses on the modification of a 160/220 bituminous binder with clay and polymer/clay nanocomposites. Bitumen/polymer/clay ternary blends were prepared using styrene–butadiene–styrene, ethylene vinyl acetate and ethylene methylacrylate copolymers mixed with an organomodified montmorillonite. Dynamic mechanical analyses were performed in the extended domain of stress, temperature and frequency to analyse the thermorheological behaviour of the blends. The time–temperature superposition principle was applied to shift the experimental data recorded at different temperatures and generate master curves of the linear viscoelastic functions. For all blends, the mechanical response of the system was found to be strongly and intimately influenced by the nanocomposite modification. In some cases, a solid-like behaviour appears and delays the Newtonian transition. Morphological analyses performed with fluorescence microscopy allowed to associate the binder properties with the presence of clay silicates, which alter the colloidal equilibrium of the bitumen and enhances the compatibility between bitumen and polymers. Based on the morphological and rheological results, a structural model of the prepared blends is proposed.     

Mapping the density of scattering centers limiting the electron mean free path in graphene

Recently, giant carrier mobility μ (>10(5) cm(2) V(-1) s(-1)) and micrometer electron mean free path (l) have been measured in suspended graphene or in graphene encapsulated between inert and ultraflat BN layers. Much lower μ values (10000-20000 cm(2) V(-1) s(-1)) are typically reported in graphene on common substrates (SiO(2), SiC) used for device fabrication. The debate on the factors limiting graphene electron mean free path is still open with charged impurities (CI) and resonant scatterers (RS) indicated as the most probable candidates. As a matter of fact, the inhomogeneous distribution of such scattering sources in graphene is responsible of nanoscale lateral inhomogeneities in the electronic properties, which could affect the behavior of graphene nanodevices. Hence, high resolution two-dimensional (2D) mapping of their density is very important. Here, we used scanning capacitance microscopy/spectroscopy to obtain 2D maps of l in graphene on substrates with different dielectric permittivities, that is, SiO(2) (κ(SiO2) = 3.9), 4H-SiC (0001) (κ(SiC) = 9.7) and the very-high-κ perovskite strontium titanate, SrTiO(3) (001), briefly STO (κ(STO) = 330). After measuring l versus the gate bias V(g) on an array of points on graphene, maps of the CI density (N(CI)) have been determined by the neutrality point shift from V(g) = 0 V in each curve, whereas maps of the RS density (N(RS)) have been extracted by fitting the dependence of l on the carrier density (n). Laterally inhomogeneous densities of CI and RS have been found. The RS distribution exhibits an average value ～3 × 10(10) cm(-2) independently on the substrate. For the first time, a clear correlation between the minima in the l map and the maxima in the N(CI) map is obtained for graphene on SiO(2) and 4H-SiC, indicating that CI are the main source of the lateral inhomogeneity of l. On the contrary, the l and N(CI) maps are uncorrelated in graphene on STO, while a clear correlation is found between l and N(RS) maps. This demonstrates a very efficient dielectric screening of CI in graphene on STO and the role of RS as limiting factor for electron mean free path.     

Tensile stress relaxation in unsaturated granular materials

The mechanics of granular media at low liquid saturation levels remain poorly understood. Macroscopic mechanical properties are affected by microscale forces and processes, such as capillary forces, inter-particle friction, liquid flows, and particle movements. An improved understanding of these microscale mechanisms is important for a range of industrial applications and natural phenomena (e.g. landslides). This study focuses on the transient evolution of the tensile stress of unsaturated granular media under extension. Experimental results suggest that the stress state of the material evolves even after cessation of sample extension. Moreover, we observe that the packing density strongly affects the efficiency of different processes that result in tensile stress relaxation. By comparing the observed relaxation time scales with published data, we conclude that tensile stress relaxation is governed by particle rearrangement and fluid redistribution. An increased packing density inhibits particle rearrangement and only leaves fluid redistribution as the major process that governs tensile stress relaxation.