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The gas flow through sheet-like porous materials such as paper can show marked lateral variations due to a heterogeneous, locally varying microstructure. Hence, reliable predictions of such lateral flux variations require an appropriate consideration of local variations in the microstructure. The flow through such sheet-like materials is commonly described with Darcy’s law in which permeances are formulated in terms of microstructure properties, such as porosities, tortuosities, or hydraulic radii. This work proposes an extension of existing permeance models that directly considers the variation and the cross-dependence between local microstructure properties. The extended model is applied to local air fluxes through a paper sheet to exemplarily reveal the joint impact of local porosities and local tortuosities on the air flux. The key extension is to consider a joint distribution of porosity and tortuosity. The latter is constructed from the univariate property distributions using a copula approach and yields local tortuosities including their variation for any encountered local porosity. These values jointly enter any permeance model that qualitatively captures the dependence of the air flux on the porosity. To assess the merit of the model, variations in the air flux and in the pore space properties are independently determined from the same measured microstructure of paper. Air flux variations are provided by computational fluid dynamics simulations on multiple, nonoverlapping segments taken from the microstructure. A statistical analysis of the entire microstructure provides the distribution of local porosity, tortuosity, and thicknesses. Our model quantitatively explains that porosity-dependent variations in the tortuosity, in particular the ones associated with high-volume pathways, decisively determine air flux variations.

The variability and interdependence of local porosity and local mean geodesic tortuosity, which is a measure for the sinuosity of shortest transportation paths, is investigated at the example of the microstructure in sack paper. By means of statistical image analysis, these two morphological characteristics are computed for several cutouts of 3D image data obtained by X-ray microcomputed tomography. Considering cutouts of different sizes allows us to study the influence of the sample size on the local variability of the considered characteristics. Moreover, the interdependence between local porosity and local mean geodesic tortuosity is quantified by modeling their joint distribution parametrically using Archimedean copulas. It turns out that the family of Gumbel copulas is an appropriate model type, which is formally validated by a goodness of fit test. Besides mean geodesic tortuosity, we consider further related morphological characteristics, describing the sinuosity of those shortest transportation paths, whose minimum diameter exceeds a predefined threshold. Moreover, we show that the copula approach investigated in this paper can also be used to quantify the negative correlation between local porosity and these modified versions of local mean geodesic tortuosity. Our results elucidate the impact of local porosity on various kinds of morphological characteristics, which are not experimentally accessible and which are important for local air permeance – a key property of sack paper.

A two-step framework to analyze local microstructure variations of paper sheets based on 3D image data is presented. First, a multi-stage workflow efficiently acquires a large set of highly resolved tomographic image data, which enables—in combination with statistical image analysis—the quantification of local variations and pairwise correlations of morphological microstructure characteristics on length scales ranging from micrometers to centimeters. Secondly, the microstructure is analyzed in terms of the local behavior of porosity, thickness, and further descriptors related to transportation paths. The power of the presented framework is demonstrated, showing that it allows one (i) to quantitatively reveal the difference in terms of local structural variations between a model paper before and after unidirectional compression via hard-nip calendering and that (ii) the field of view which is required to reliably compute the probability distributions of the considered local microstructure characteristics is at least 20 mm$^{2}$. The results elucidate structural differences related to local densification. In particular, it is shown how calendering transforms local variations in sheet thickness into marked local mass density variations. The obtained results are in line with experimental measurements of macroscopic properties (basis weight, Bekk smoothness parameters, thickness, and Gurley retention times).

In this Letter, we explore the potential energy surface (PES) of the 3 × 3 C-face of SiC by means of the density functional theory. Following an extensive and intuitive exploration, we propose a model for this surface reconstruction based on an all-silicon over-layer forming an ordered honeycomb-Kagome network. This model is compared to the available scanning tunneling microscope (STM) topographies and conductance maps. Our STM simulations reproduce the three main characteristics observed in the measurements, revealing the underlying complex and hybrid passivation scheme. Indeed, below the ordered over-layer, the competition between two incompatible properties of silicon induces a strong disorder in the charge transfer between unpassivated dangling bonds of different chemistry. This effect in conjunction with the glassy-like character of the PES explains why it has taken decades to provide an accurate atomistic representation for this structure.

Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 A. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

International audience; The structure of the ultimately-thin crystalline allotrope of silicon oxide, prepared onto a ruthenium surface, is unveiled down to atomic scale with chemical sensitivity, thanks to high resolution scanning tunneling microscopy and first principle calculations. An ordered oxygen lattice is imaged which coexists with the two-dimensional monolayer oxide. This coexistence signals a displacive transformation from an oxygen reconstructed-Ru(0001) to silicon oxide, along which latterally-shifted domains form, each with equivalent and degenerate epitaxial relationships with the substrate. The unavoidable character of defects at boundaries between these domains appeals for the development of alternative methods capable of producing single-crystalline two-dimensional oxides.

Here we investigate Ge mixing at the Si(001) surface and characterize the 2 N Si(001) reconstruction by means of hybrid quantum and molecular mechanics calculations (QM/MM). Avoiding fake elastic dampening, this scheme allows to correctly take into account long range deformation induced by reconstructed and defective surfaces. We focus in particular on the dimer vacancy line (DVL) and its interaction with Ge adatoms. We first show that calculated formation energies for these defects are highly dependent on the choice of chemical potential and that the latter must be chosen carefully. Characterizing the effect of the DVL on the deformation field, we also find that the DVL favors Ge segregation in the fourth layer close to the DVL. Using the activation-relaxation technique (ART nouveau) and QM/MM, we show that a complex diffusion path permits the substitution of the Ge atom in the fourth layer, with barriers compatible with mixing observed at intermediate temperature. We also show that the use of QM/MM results in much more signi cant corrections at the saddle points (up to 0.5 eV) that at minima, demonstrating its importance for describing kinetics correctly.

The evolution of many systems is dominated by rare activated events that occur on timescale ranging from nanoseconds to the hour or more. For such systems, simulations must leave aside the full thermal description to focus specifically on mechanisms that generate a configurational change. We present here the activation relaxation technique (ART), an open-ended saddle point search algorithm, and a series of recent improvements to ART nouveau and kinetic ART, an ART-based on-the-fly off-lattice self-learning kinetic Monte Carlo method.

We have studied the crystal and electronic structure of monoclinic (MC) InSe under pressure finding a reversible phase transition to a ${\mathrm{Hg}}_{2}{\mathrm{Cl}}_{2}$-like tetragonal phase. The pressure evolution of the crystal structure was investigated by angle-dispersive x-ray diffraction and Raman spectroscopy in a diamond-anvil cell up to $30\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. From the diffraction experiments, we deduced that MC InSe becomes gradually more symmetric under pressure, transforming the crystal structure into a tetragonal one at $19.4\ifmmode\pm\else\textpm\fi{}0.5\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. This phase transition occurs without any volume change. Raman measurements under pressure confirmed the occurrence of a monoclinic-to-tetragonal transformation. The nondegenerate modes in the MC phase, especially the ${A}_{g}^{4}$ modes, exhibit a negative pressure coefficient, converging with the ${B}_{g}^{1}$ modes, and becoming an $Eg$ mode in the tetragonal phase. The experimental results are interpreted through density-functional theory (DFT) electronic-structure and total-energy calculations, which showed that beyond $18\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ the tetragonal phase is the most stable phase. It is also shown that along the continuous change from monoclinic to tetragonal InSe, there is a progressive decrease of the band gap and eventually, in the tetragonal phase, there occurs a small band overlap. However, the Raman-effect and optical-absorption measurements suggest that this overlap is probably due to the usual DFT band-gap underestimation. Tetragonal InSe is most likely a low-gap semiconductor. The bonding in the monoclinic phase and that in the tetragonal InSe phase are compared.

The electronic structure of different polymorphs of gallium sulphide $(\mathrm{GaS})$ with cubic structure is investigated by means of first-principles band structure calculations in connection with experimental reports on a metastable semiconducting cubic form of this material. The expected metallic character of simple cubic phases containing one $\mathrm{GaS}$ group per unit cell (rocksalt or zinc-blende) is confirmed by the calculations. A cubane-based zinc-blende structure is found to exhibit a band gap which is compatible with experimental results but the unit cell parameter is much larger than the reported ones. We have also studied cubic phases containing hydrogen. It is found that two insulating polymorphs can be stable: (i) a simple cubic structure based on $[\mathrm{HGaS}{]}_{4}$ cubane units and (ii) an insulating zinc-blende structure in which hydrogen atoms occupy the empty sites of the cubic unit cell. The last structure seems to be the more likely structural alternative for the phase so far described as a semiconducting cubic phase of $\mathrm{GaS}$. The presence of hydrogen could explain the reported instability of cubic $\mathrm{GaS}$ under thermal annealing.

We have performed single crystal angle dispersive X-ray diffraction at high pressure in order to investigate the GaS and InSe equations of state. We situate the transition from β-GaS to GaS-II at 2 7 0 3. ± . GPa. In the InSe experiment we locate the beginning of the phase transition at 7.6 ± 0.6 GPa. The equations of state of β-GaS ( 0 43 27 0 06V = . ± . Å 3 , 37 2 GPaB = ± , 5 2B = .¢ ), GaS-II ( 0 42 4 0 2V = . ± . Å 3 , 50 3 GPaB = ± and 4 3 0 3B = . ± .¢ ) and γ-InSe ( 0 58 4 0 2V = . ± . Å 3 , 24 3 GPaB = ± and 8 6 0 8B = . ± .¢ ) are discussed and compared with the results of an ab-initio calculation.

In this letter, we study the stability of the domain model for lithium intercalated graphite in stages III and II by means of Density Functional Theory and Kinetic Lattice Monte Carlo simulations. We find that the domain model is either thermodynamically or kinetically stable when compared to the standard model in stages III and II. The existence of domains in the intercalation sequence is well supported by recent high resolution transmission electron microscope observations in lithiated graphite. Moreover, we predict that such domain staging sequences leads to a wide range of diffusivity as reported in experiments.

Magnetism in two dimensional atomic sheets has attracted considerable interest as its existence could allow the development of electronic and spintronic devices. The existence of magnetism is not sufficient for devices, however, as states must be addressable and modifiable through the application of an external drive. We show that defects in hexagonal boron nitride present a strong interplay between the N-N distance in the edge and the magnetic moments of the defects. By stress-induced geometry modifications, we change the ground state magnetic moment of the defects. This control is made possible by the triangular shape of the defects as well as the strong spin localisation in the magnetic state.

Unbiased open-ended methods for finding transition states are powerful tools to understand diffusion and relaxation mechanisms associated with defect diffusion, growth processes, and catalysis. They have been little used, however, in conjunction with ab initio packages as these algorithms demanded large computational effort to generate even a single event. Here, we revisit the activation-relaxation technique (ART nouveau) and introduce a two-step convergence to the saddle point, combining the previously used Lanczós algorithm with the direct inversion in interactive subspace scheme. This combination makes it possible to generate events (from an initial minimum through a saddle point up to a final minimum) in a systematic fashion with a net 300-700 force evaluations per successful event. ART nouveau is coupled with BigDFT, a Kohn-Sham density functional theory (DFT) electronic structure code using a wavelet basis set with excellent efficiency on parallel computation, and applied to study the potential energy surface of C(20) clusters, vacancy diffusion in bulk silicon, and reconstruction of the 4H-SiC surface.