No Arabic abstract
Celitement is a new type of cement that is based on hydraulic calcium-hydrosilicate (hCHS) that possesses a potential for minimizing the ratio C/S from above 3 in OPC down to 1, which significantly reduces the amount of CO$_2$ released during processing. The reaction kinetics of hCHS differs from that of classical clinker phases due to the presence of highly reactive silicate species, which involve silanol groups instead of pure calcium silicates and aluminates and aluminoferrites. In contrast to Portland cement, no calcium hydroxide is formed during hydration, which otherwise regulates the Ca concentration. Without the buffering role of Ca(OH)$_2$ the concentration of the dissolved species c(Ca$^{2+}$) and c(SiO$_4^{4-}$) and the corresponding pH must be controlled to ensure a reproducible reaction. Pure hCHS reacts isochemically with water, resulting in a C-S-H phase with the same chemical composition as a single hydration product, with a homogeneous distribution of the main elements Ca and Si throughout the sample. Here we study via nanoindentation the mechanical properties of two different types of hardened pastes made out of Celitement (C/S=1.28), with varying amounts of hCHS and variable water to cement ratio. We couple nanoindentation grids with Raman mappings to link the nanoscale mechanical properties to individual microstructural components, yielding in-depth insight into the mechanics of the mineralogical phases constituting the hardened cement paste. We show that we can identify in hardened Celitement paste both fresh C-S-H with varying density, and C-S-H from the raw material using their specific Raman spectra, while simultaneously measuring their mechanical properties. Albeit not suitable for phase identification, EDX measurements provide valuable information about the distribution of alkalis, thus further helping to understand the reaction pattern of hCHS.
In this paper, the implementation of optical elements in the form of Pancharatnam-Berry optics is considered. With respect to 3D bulk and diffractive optics, acting on the dynamic phase of light, Pancharatnam-Berry optical elements transfer a phase which is geometric in nature by locally manipulating the polarization state of the incident beam. They can be realized as space-variant sub-wavelengths gratings that behave like inhomogeneous form-birefringent materials. We present a comprehensive work of simulation, realization, and optical characterization at the telecom wavelength of 1310 nm of the constitutive linear grating cell, whose fabrication has been finely tuned in order to get a {pi}-phase delay and obtain a maximum in the diffraction efficiency. The optical design in the infrared region allows the use of silicon as candidate material due to its transparency. In order to demonstrate the possibility to assemble the single grating cells for generating more complex phase patterns, the implementation of two Pancharatnam-Berry optical elements is considered: a blazed grating and an optical vortices demultiplexer.
Polycrystalline ceramic samples and a single crystal of EuTiO3 have been investigated by Raman spectroscopy in the temperature range 80-300 K. Although synchrotron XRD data clearly indicated the cubic to tetragonal phase transition around 282 K, no mode from the symmetry allowed Raman active phonons was found in the tetragonal phase, contrary to the case of the homologous SrTiO3. In order to study the evolution of this unique characteristic, ceramics of EuxSr1-xTiO3 (x=0.03-1.0) characterized by synchrotron XRD for the structural phase transition have been also investigated by Raman spectroscopy, verifying the very strong influence on the Raman yield by Eu substitution. By applying an external magnetic field or alternatively hydrostatic pressure modes are activated in the Raman spectra. The temperature dependence of the main mode that is activated shows remarkable agreement with theoretical predictions. We attribute the puzzling absence of the Raman modes to a mechanism related to strong spin-lattice interaction that drives the cubic to tetragonal structural phase transition and makes the Raman tensor antisymmetric. On the contrary, the external perturbations induce a symmetric Raman tensor allowing even symmetry modes to be present in the spectra. Previous EPR, muon scattering and magnetic measurements indicated the presence of small magnetic interactions deep inside the paramagnetic phase. In order to probe those magnetic interactions in our EuTiO3 polycrystalline sample and test our hypothesis, we have performed temperature dependant XAS/XMCD, which support the existence of magnetic nanodomains even close to room temperature.
Antiferromagnets (AFMs) with zero net magnetization are proposed as active elements in future spintronic devices. Depending on the critical thickness of the AFM thin films and the measurement temperature, bimetallic Mn-based alloys and transition metal oxide-based AFMs can host various coexisting ordered, disordered, and frustrated AFM phases. Such coexisting phases in the exchange coupled ferromagnetic (FM)/AFM-based heterostructures can result in unusual magnetic and magnetotransport phenomena. Here, we integrate chemically disordered AFM IrMn3 thin films with coexisting AFM phases into complex exchange coupled MgO(001)/Ni3Fe/IrMn3/Ni3Fe/CoO heterostructures and study the structural, magnetic, and magnetotransport properties in various magnetic field cooling states. In particular, we unveil the impact of rotating the relative orientation of the disordered and reversible AFM moments with respect to the irreversible AFM moments on the magnetic and magnetoresistance properties of the exchange coupled heterostructures. We further found that the persistence of AFM grains with thermally disordered and reversible AFM order is crucial for achieving highly tunable magnetic properties and multi-level magnetoresistance states. We anticipate that the introduced approach and the heterostructure architecture can be utilized in future spintronic devices to manipulate the thermally disordered and reversible AFM order at the nanoscale.
Photo-Induced Enhanced Raman Spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with an order-of-magnitude Raman signal enhancement of adsorbed analytes over that of typical SERS substrates. Despite the impressive PIERS enhancement factors and explosion in recent demonstrations of its utility, the detailed enhancement mechanism remains undetermined. Using a range of optical and X-ray spectroscopies, supported by density functional theory calculations, we elucidate the chemical and atomic-scale mechanism behind the PIERS enhancement. Stable PIERS substrates with enhancement factors of 10^6 were fabricated using self-organized hexagonal arrays of TiO2 nanotubes that were defect-engineered via annealing in inert atmospheres, and silver nanoparticles were deposited by magnetron sputtering and subsequent thermal dewetting. We identified the key source of the enhancement of PIERS vs. SERS in these structures as an increase in the Raman polarizability of the adsorbed probe molecule upon photo-induced charge transfer. A balance between crystallinity, which enhances charge transfer due to higher electron mobility in anatase-rutile heterostructures but decreases visible light absorption, and oxygen vacancy defects, which increase visible light absorption and photo-induced electron transfers, was critical to achieve high PIERS enhancements.
We present a new approach to femtosecond direct laser writing lithography to pattern nanocavities in ferromagnetic thin films. To demonstrate the concept we irradiated 300~nm thin nickel films by single intense femtosecond laser pulses through the glass substrate and created complex surface landscapes at the nickel-air interface. Using a fluence above the ablation threshold the process is destructive and irradiation leads to the formation of 200~nm thin flakes of nickel around the ablation crater as seen by electron microscopy. By progressively lowering the peak laser fluence, slightly below the ablation threshold the formation of closed spallation cavities is demonstrated by interferometric microscopy. Systematic studies by electron and optical interferometric microscopies enabled us to gain an understanding of the thermo-mechanical mechanism leading to spallation at the solid-molten interface, a conclusion supported by molecular dynamics simulations. We achieved a control of the spallation process that enabled the fabrication of closed spallation nanocavities and their periodic arrangements. Due to their topology closed magnetic nanocavities can support unique couplings of multiple excitations (magnetic, optical, acoustic, spintronic). Thereby, they offer a unique physics playground, before unavailable, for magnetism, magneto-photonic and magneto-acoustic applications.