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Additively manufactured hollow-strut bioceramic scaffolds present a promising strategy towards enhanced performance in patient-tailored bone tissue engineering. The channels in such scaffolds offer pathways for nutrient and cell transport and facilitate effective osseointegration and vascularization. In this study, we report an approach for the slurry based additive manufacturing of modified diopside bioceramics that enables the production of hollow-strut scaffolds with diverse cross-sectional forms, distinguished by different configurations of channel and strut geometries. The prepared scaffolds exhibit levels of porosity and mechanical strength that are well suited for osteoporotic bone repair. Mechanical characterization in orthogonal orientations revealed that a square outer cross-section for hollow struts in woodpile scaffolds gives rise to levels of compressive strength that are higher than those of conventional solid cylindrical strut scaffolds despite a significantly lower density. Finite element analysis confirms that this improved strength arises from lower stress concentration in such geometries. It was shown that hollow struts in bioceramic scaffolds dramatically increase cell attachment and proliferation, potentially promoting new bone tissue formation within the scaffold channel. This work provides an easily controlled method for the extrusion-based 3D printing of hollow strut scaffolds. We show here how the production of hollow struts with controllable geometry can serve to enhance both the functional and mechanical performance of porous structures, with particular relevance for bone tissue engineering scaffolds.

Mixed phase materials in the quasi binary diopside (CaMgSi2O6) – molybdite (MoO3) system were synthesized by a precipitation method. Materials were fabricated with diopside to molybdite ratios of 1:0, 10:1, 5:1, 2:1 and 1:1. XRD, SEM and EDS results show that alongside the initial diopside phase, phases such as calcium molybdate CaMoO4, rod-like enstatite MgSiO3 and cristobalite SiO2 formed as the molybdite content increased, and diopside was entirely absent at the highest molybdite content. At lower Mo content, mixed phase materials showed higher hardness and slower biodegradation in SBF relative to pristine diopside, while maintaining reasonable hydroxyapatite (HAp) formation capability. In contrast, materials with higher molybdite content exhibited lower hardness and bioactivity. The variation in the mechanical and bioactive performance could be attributed to the presence of bulk CaMoO4, acting as a reinforcement, and rod-like MgSiO3 with a highly porous and fragile structure. The trend of hardness is not consistent to the proportion of the component phases could be attributed to morphologies, interfaces, and densities of the samples. Both of secondary phases had poorer HAp deposition compared to pure diopside, indicating the MoO3 addition lowered mixed phase CaMgSi2O6 – MoO3 bioceramics’ ability to form Hap. The results suggest that moderate addition of molybdite to diopside would be an effective pathway towards crystalline bioceramics with enhanced performance.

Finding effective cathode materials is currently one of the key barriers to the development of magnesium batteries, which offer enticing prospects of larger capacities alongside improved safety relative to Li-ion batteries. Here, we report the hydrothermal synthesis of several types of WS2 nanostructures and their performance as magnesium battery cathodes. The morphology of WS2 materials was controlled through the use of sodium oxalate as a complexing agent and different templating agents, including polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and hexadecyltrimethyl ammonium bromide (CTAB). A high capacity of 142.7 mAh/g was achieved after 100 cycles at a high current density of 500 mA/g for cathodes based on a nanostructured flower-like WS2. A solution consisting of magnesium (II) bis(trifluoromethanesulfonyl)imide (MgTFSI2) and magnesium (II) chloride (MgCl2) in dimethoxyethane (DME) was used as an effective electrolyte, which contributes to favorable Mg2+ mobility. Weaker ionic bonds and van der Waals forces of WS2 compared with other transition metal oxides/sulfides lay the foundation for fast discharge/charge rate. The enhanced surface area of the nanostructured materials plays a key role in enhancing both the capacity and discharge/charge rate.

Anatase thin films spin coated on soda–lime–silica (SLS) glass and unpolished (001) rutile were annealed at 200–550 °C for 8 h, followed by GAXRD, Raman, XPS, SIMS, AFM, TEM, UV–Vis, ellipsometry, and MB dye degradation. Films on SLS substrates annealed at 200–350 °C were amorphous but those annealed at 450°–550 °C consisted of anatase; the rutile substrates gave epitaxial rutile films. Annealing caused diffusion of glass ions into the films and counterdiffusion of Ti into the glass substrates. The decrease in glass ion concentrations during aqueous MB testing shows that grain boundary diffusion occurred. The AFM, TEM, and UV–Vis data were affected by the substrate topographies, where SLS was smooth and rutile was rough/uneven. Decreasing Eg in the anatase films with increasing annealing temperature was attributed to increasing crystallinity (heterogeneous nucleation) while the same effect in the rutile films was attributed to the substrate topography (homogeneous nucleation). The anatase films photocatalytically outperformed the rutile films; this was attributed to the potential to form midgap states from oxygen vacancy formation and/or Ti vacancy formation (deriving from the Ti counter-diffusion). However, the deep energy levels of these defects suggest that the performance is dominated by the crystallinity and blockage of the active sites.

The significance of the spin-orbit interaction is very well known in compounds containing heavier elements such as the rare-earth Eu ion. Here, through density functional calculations, we investigated the effect of the spin-orbit interaction on the magnetic ground state of Eu doped magnetite ($\mathrm{Fe_3O_4:Eu_{Fe}}$). By examining all possible spin alignments between Eu and magnetite's Fe, we demonstrate that Eu, which is most stable when doped at the tetrahedral site, adapts a spin almost opposite the substituted Fe. Consequently, because of smaller spin cancellation between the cations on the tetrahedral site ($\mathrm{Fe_{Tet}}$ and $\mathrm{Eu_{Tet}}$) and the cations on the octahedral sites ($\mathrm{Fe_{Oct}}$), $\mathrm{Fe_3O_4:Eu_{Fe}}$ exhibits a maximum saturation magnetisation of 9.451 $\mu_B/$f.u. which is significantly larger than that of undoped magnetite (calculated to be 3.929 $\mu_B/$f.u.). We further show that this large magnetisation persists through additional electron doping. However, additional hole doping, which may unintentionally occur in Fe deficient magnetite, can reduce the magnetisation to values smaller than that of the undoped magnetite. The results presented here can aid in designing highly efficient magnetically recoverable catalysts for which both magnetite and rare earth dopants are common materials., Comment: 12 pages, 9 figures, 3 tables

Normal contact behaviour between non-adhesive fractal rough particles is studied using a finite element method (FEM). A series of spherical grain surfaces with distinguished roughness features are generated by means of Spherical Harmonics. These surfaces are described by two roughness descriptors, namely, relative roughness (Rr) and fractal dimension (FD). The contact behaviour of rough spheres with a rigid flat surface is simulated using FEM to quantify the influences of surface structure and sphere morphology by focusing on contact stiffness and true contact area. The dependence of normal contact stiffness (k) on applied normal force (F) is found to follow a power law (k = αFβ) over four orders of magnitude, with both α and β being highly correlated with Rr and FD. With increasing load, the power exponent converges to that of Hertzian contact, e.g., 1/3, independent of Rr. Regions of true contact evolve through the formation of new microcontacts and their progressive merging, meanwhile the area distributions of contact island induced by various forces tend to obey similar Weibull distributions due to fractal nature in their surfaces. Contacts with larger values of Rr are found to produce contact contours with higher fractal dimension as calculated by a 2D box-counting method. Our results suggest that the correlation between radial lengths in a quasi-spherical particle should be considered in studying contact behaviour.

Through comprehensive density functional calculations, we predict the stability of a rhenium-based ferrite, ReFe2O4, in a distorted spinel-based structure. In ReFe2O4, all Re and half of the Fe ions occupy the octahedral sites while the remaining Fe ions occupy the tetrahedral sites. All Re ions are predicted to be at a + 4 oxidation state with a low spin configuration (S = 3/2), while all Fe ions are predicted to be at a + 2 oxidation state with a high-spin state configuration (S = 2). Magnetically, ReFe2O4adopts an unconventional ferrimagnetic state in which the magnetic moment of Re opposes the magnetic moments of both tetrahedral and octahedral Fe ions. The spin–orbit coupling is found to cause a slight spin canting of ~ 1.5°. The predicted magnetic ground state is unlike the magnetic alignment usually observed in ferrites, where the tetrahedral cations oppose the spin of the octahedral cations. Given that the density of states analysis predicts a half-metallic character driven by the presence of Ret2gstates at the Fermi level, this compound shows promise towards potential spintronics applications.

International audience; Here we introduce a versatile stereolithographic route to produce three different kinds of Si-containing thermosets that yield high performance ceramics upon thermal treatment. Our approach is based on a fast and inexpensive thiol-ene free radical addition that can be applied for different classes of preceramic polymers with carbon-carbon double bonds. Due to the rapidity and efficiency of the thiol-ene click reactions, this additive manufacturing process can be effectively carried out using conventional light sources on benchtop printers. Through light initiated cross-linking, the liquid preceramic polymers transform into stable infusible thermosets that preserve their shape during the polymer-to-ceramic transformation. Through pyrolysis the thermosets transform into glassy ceramics with uniform shrinkage and high density. The obtained ceramic structures are nearly fully dense, have smooth surfaces, and are free from macroscopic voids and defects. A fabricated SiOC honeycomb was shown to exhibit a significantly higher compressive strength to weight ratio in comparison to other porous ceramics.

To develop high emissivity coatings on fibrous ceramic substrates with improved thermal resistance for reusable space systems, WSi2-MoSi2-Si-SiB6-borosilicate glass coatings were prepared on fibrous ZrO2 by slurry dipping and subsequent high temperature rapid sintering. A coating with 50 wt% WSi2 and 50 wt% MoSi2 presents optimal thermal stability with only 10.06 mg/cm2 mass loss and 4.0 % emissivity decrease in the wavelength regime of 1.27 to 1.73 microns after 50 h oxidation at 1773 K. The advantages of double phase metal silicide coatings combining WSi2 and MoSi2 include improved thermal compatibility with the substrate and an enhanced glass mediated self healing ability.

Hypothesis Control of capillary flow through porous media has broad practical implications. However, achieving accurate and reliable control of such processes by tuning the pore size or by modification of interface wettability remains challenging. Here we propose that the flow of liquid by capillary penetration can be accurately adjusted by tuning the geometry of porous media and develop numerical method to achieve this. Methodologies On the basis of Darcys law, a general framework is proposed to facilitate the control of capillary flow in porous systems by tailoring the geometric shape of porous structures. A numerical simulation approach based on finite element method is also employed to validate the theoretical prediction. Findings A basic capillary component with a tunable velocity gradient is designed according to the proposed framework. By using the basic component, two functional capillary elements, namely, (i) flow amplifier and (ii) flow resistor, are demonstrated. Then, multi functional fluidic devices with controllable capillary flow are realized by integrating the designed capillary elements. All the theoretical designs are validated by numerical simulations. Finally, it is shown that the proposed model can be extended to three dimensional designs of porous media

International audience; Tribological phenomena are governed by combined effects of material properties, topology and surface-chemistry. We study the interplay of multiscale-surface-structures with molecular-scale interactions towards interpreting static frictional interactions at fractal interfaces. By spline-assisted-discretization we analyse asperity interactions in pairs of contacting fractal surface profiles. For elastically deforming asperities, force analysis reveals greater friction at surfaces exhibiting higher fractality, with increasing molecular-scale friction amplifying this trend. Increasing adhesive strength yields higher overall friction at surfaces of lower fractality owing to greater true-contact-area. In systems where adhesive-type interactions play an important role, such as those where cold-welded junctions form, friction is minimised at an intermediate value of surface profile fractality found here to be in the regime 1.3-1.5. Our results have implications for systems exhibiting evolving surface structures.https://doi.org/10.1016/j.triboint.2015.09.016; Les phénomènes tribologiques sont régis par les effets combinés des propriétés des matériaux, de la topologie et de la chimie des surfaces. Nous étudions l’interaction des structures de surface multi-échelles avec les interactions à l’échelle moléculaire pour interpréter les interactions frictionnelles statiques aux interfaces fractales. Par discrétisation assistée par spline, nous analysons les interactions d’asperité par paires de profils de surface fractale en contact. Pour les aspérités se déformant élastiquement, l'analyse de la force révèle un frottement plus important sur les surfaces présentant une fractalité plus élevée, le frottement croissant à l'échelle moléculaire amplifiant cette tendance. L'augmentation de la force adhésive engendre un frottement global plus élevé sur les surfaces de fractalité inférieure en raison d'une plus grande surface de contact. Dans les systèmes où les interactions de type adhésif jouent un rôle important, tels que ceux où se forment des jonctions soudées à froid, le frottement est minimisé à une valeur intermédiaire de la fractalité du profil de surface qui se situe autour de 1,3–1,5. Les résultats ont des implications pour les systèmes présentant des structures de surface en évolution.https://doi.org/10.1016/j.triboint.2015.09.016

International audience; Silicate ceramics are of considerable promise as high frequency dielectrics in emerging millimetre wave applications including high bandwidth wireless communication and sensing. In this review, we show how high quality factors and low, thermally stable permittivities arise in ordered silicate structures. On the basis of a large number of existing studies, the dielectric performance of silicate ceramics is comprehensively summarised and presented, showing how microstructure and SiO4 tetrahedral connectivity affect polarizability and dielectric losses. We critically examine the appropriateness of silicate materials in future applications as effective millimetre wave dielectrics with low losses and tuneable permittivities. The development of new soft chemistry based processing routes for silicate dielectric ceramics is identified as being instrumental towards the reduction of processing temperatures, thus enabling silicate ceramics to be co-fired in the production of components functioning in the mm wave regime.

International audience; Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), synthesised through the acidic condensation of 1,3-bis(3-(triethoxysilyl)propyl)urea (BTPU). Experimentally, we show that POSS-urea has excellent functionality for molecular recognition toward acetonitrile with an adsorption level of 74 mmol/g, which compares favourably to MOFs and zeolites, with applications in volatile organic compounds (VOC). The acetonitrile adsorption capacity was 132-fold higher relative to adsorption capacity for toluene, which shows the pores are highly selective towards acetonitrile adsorption due to their size and arrangement. Theoretically, our tight-binding density functional and molecular dynamics calculations demonstrated that this BTPU based POSS is microporous with an irregular placement of the pores. Structural studies confirm maximal pore sizes of ~ 1 nm, with POSS cages possessing an approximate edge length of ~ 3.16 Å.

International audience; The water-gas shift reaction (WGS) is important and widely applied in the production of H2. Cu-modified perovskites are promising catalysts for WGS reactions in hydrogen generation. However, the structure-dependent stability and reaction pathways of such materials remain unclear. Herein, we report catalytically active Cu-modified SrTiO3 (nominally SrTi1−xCuxO3) prepared by a modified polymeric precursor method. Microstructural analysis revealed a partially segregated CuO phase in the as-prepared materials. Operando X-ray diffraction and absorption spectroscopy showed the reduction of CuO into a stable metallic phase under conditions of WGS reactions for all compositions. Among the characterized materials, the x = 0.20 composition showed the highest turnover frequency, lowest activation energy, and the highest WGS rate at 300 °C. According to density functional calculations, the formation of CuO is energetically less favorable compared with, SrTiO3, explaining why the segregated CuO phase on the SrTiO3 surface is reduced to Cu during the catalytic reaction, while SrTiO3 remains. For x = 0.20, the size of the segregated CuO phase is optimum for facilitating the catalytic reaction. In contrast, a higher Cu content (x = 0.3) results in an aggregation of smaller CuO particles, resulting in fewer surface active sites and a net decrease in catalytic performance.

International audience; Freeze casting, also known as ice templating, is a particularly versatile technique that has been applied extensively for the fabrication of well‐controlled biomimetic porous materials based on ceramics, metals, polymers, biomacromolecules, and carbon nanomaterials, endowing them with novel properties and broadening their applicability. The principles of different directional freeze‐casting processes are described and the relationships between processing and structure are examined. Recent progress in freeze‐casting assisted assembly of low dimensional building blocks, including graphene and carbon nanotubes, into tailored micro‐ and macrostructures is then summarized. Emerging trends relating to novel materials as building blocks and novel freeze‐cast geometries—beads, fibers, films, complex macrostructures, and nacre‐mimetic composites—are presented. Thereafter, the means by which aligned porous structures and nacre mimetic materials obtainable through recently developed freeze‐casting techniques and low‐dimensional building blocks can facilitate material functionality across multiple fields of application, including energy storage and conversion, environmental remediation, thermal management, and smart materials, are discussed.; (traduit par un robot)La coulée sous pression, également connue sous le nom de modèle de glace, est une technique particulièrement polyvalente qui a été largement appliquée pour la fabrication de matériaux poreux biomimétiques bien contrôlés à base de céramique, de métaux, de polymères, de biomacromolécules et de nanomatériaux de carbone, leur conférant de nouvelles propriétés et leur élargissement. leur applicabilité. Les principes des différents processus de coulée sous pression directionnelle sont décrits et les relations entre le traitement et la structure sont examinées. Les progrès récents dans l'assemblage assisté par coulée sous pression de blocs de construction de faible dimension, y compris le graphène et les nanotubes de carbone, en micro et macrostructures sur mesure sont ensuite résumés. Les tendances émergentes concernant les nouveaux matériaux comme les blocs de construction et les nouvelles géométries coulées sous pression - perles, fibres, films, macrostructures complexes et composites mimétiques de nacre - sont présentées. Par la suite, les moyens par lesquels les structures poreuses alignées et les matériaux mimétiques de nacre pouvant être obtenus par le biais de techniques de coulée sous pression et de blocs de construction de faible dimension récemment développés peuvent faciliter la fonctionnalité des matériaux dans de multiples domaines d'application, y compris le stockage et la conversion d'énergie, l'assainissement de l'environnement, la gestion thermique et les matériaux intelligents sont discutés.

Hydroxyapatite (HA) synthesized by a wet chemical route was subjected to heavy ion irradiation, using 4 MeV Krypton ion (Kr17+) with ion fluence ranging from 1 × 1013 to 1 × 1015 ions/cm2. Glancing incidence X-ray diffraction (GIXRD) results confirmed the phase purity of irradiated HA with a moderate contraction in lattice parameters, and further indicated the irradiation-induced structural disorder, evidenced by broadening of the diffraction peaks. High-resolution transmission electron microscopy (HRTEM) observations indicated that the applied Kr irradiation induced significant damage in the hydroxyapatite lattice. Specifically, cavities were observed with their diameter and density varying with the irradiation fluences, while a radiation-induced crystalline-to-amorphous transition with increasing ion dose was identified. Raman and X-ray photoelectron spectroscopy (XPS) analysis further indicated the presence of irradiation-induced defects. Ion release from pristine and irradiated materials following immersion in Tris (pH 7.4, 37 ℃) buffer showed that dissolution in vitro was enhanced by irradiation, reaching a peak at 0.1dpa. We examined the effects of irradiation on the early stages of the mouse osteoblast-like cells (MC3T3-E) response. A cell counting kit-8 assay (CCK-8 test) was carried out to investigate the cytotoxicity of samples, and viable cells can be observed on the irradiated materials.

As a typical multiphase fluid flow process, drainage in porous media is of fundamental interest in nature and industrial applications. During drainage processes in unsaturated soils and porous media in general, saturated clusters, in which a liquid phase fully occupies the pore space between solid grains, affect the relative permeability and effective stress of the system. In this study, we experimentally studied drainage processes in unsaturated granular media as a model porous system. The distribution of saturated clusters is analysed by an optical imaging method under different drainage conditions, in which pore-scale information from Voronoi and Delaunay tessellation was used to characterise the topology of saturated cluster distributions. By employing statistical analyses, the observed spatial and temporal information of multiphase flow and fluid entrapment in porous media are described. The results indicate that the distributions of both the crystallised cell size and pore size are positively correlated to the spatial and temporal distribution of saturated cluster sizes. The saturated cluster size is found to follow a lognormal distribution, in which the generalised Bond number correlates negatively to the scale parameter and positively to the shape parameter. These findings can be used to connect pore-scale behaviour with overall hydro-mechanical characteristics in partially saturated porous media, using both the degree of saturation and generalised Bond number., Comment: 18 pages, 6 figures

In this paper, we study the contact stiffness of a fractal rough surface compressed by a rigid flat plane. A numerical model based on the analysis of flat punch indentation is proposed for simulated hierarchical surfaces, which are generated using statistical and fractal descriptors collected by surface profilometry. The contact stiffness of surfaces under increasing normal load is determined on the basis of the total truncated area at varying heights. The results are compared with experimental data from nanoindentation on four types of treated rough surfaces, showing good agreement with experimental observations below a certain truncation depth. Furthermore, the limits of the model's validity are discussed by focusing on surface geometries and deformation of contacting asperities. With this proposed truncation method, we present a parametric analysis to establish a correlation between contact stiffness and surface roughness descriptors. The contact stiffness shows a unified power-law scaling with respect to the applied load over a wide range for simulated surfaces with distinct sets of roughness descriptors. The exponent of the power-law relationship is found to correlate positively to the fractal dimension while its amplitude is inversely correlated to the surface roughness amplitude. This study provides an easily implemented and computationally efficient method to connect mechanical behaviour with multi-scale surface structure, which can be utilized in design and optimization of engineering applications involving rough contacts.

Lithium ceramics have been considered as tritium breeder materials in many proposed designs of fusion breeding blankets. Heat generated in breeder pebble beds due to nuclear breeding reaction must be removed by means of actively cooled plates while generated tritiums is recovered by purge gas slowly flowing through beds. Therefore, the effective thermal conductivity of pebble beds that is one of the governing parameters determining heat transport phenomenon needs to be addressed with respect to mechanical status of beds and purge gas pressure. In this study, a numerical framework combining finite element simulation and a semi-empirical correlation of gas gap conduction is proposed to predict the effective thermal conductivity. The purge gas pressure is found to vary the effective thermal conductivity, in particular with the presence of various sized gaps in pebble beds. Random packing of pebble beds is taken into account by an approximated correlation considering the packing factor and coordination number of pebble beds. The model prediction is compared with experimental observation from different sources showing a quantitative agreement with the measurement.

In water treatment applications, the use of ceramic membranes is associated with numerous advantages relative to polymer-based filtration systems. High-temperature stability, fouling resistance, and low maintenance requirements contribute to lower lifecycle costs in such systems. However, the high production costs of most commercially available ceramic membranes, stemming from raw materials and processing, are uneconomical for such systems in most water treatment applications. For this reason, there is a growing demand for new ceramic membranes based on low-cost raw materials and processes. The use of unrefined mineral feedstocks, clays, cement, sands, and ash as the basis for the fabrication of ceramic membranes offers a promising pathway towards the obtainment of effective filtration systems that can be economically implemented in large volumes. The design of effective ceramic filtration membranes based on low-cost raw materials and energy-efficient processes requires a balance of pore structure, mass flow, and robustness, all of which are highly dependent on the composition of materials used, the inclusion of various pore-forming and binding additives, and the thermal treatments to which membranes are subjected. In this review, we present recent developments in materials and processes for the fabrication of low-cost membranes from unrefined raw materials, including clays, zeolites, apatite, waste products, including fly ash and rice husk ash, and cement. We examine multiple aspects of materials design and address the challenges relating to their further development.

The hydrophobicity of CeO2 surfaces is examined here. Since wettability measurements are extremely sensitive to experimental conditions, we propose a general approach to obtain contact angles between water and ceria surfaces of specified orientations based on density functional calculations. In particular, we analysed the low index surfaces of this oxide to establish their interactions with water. According to our calculations, the CeO2 (111) surface was the most hydrophobic with a contact angle of {\Theta} = 112.53{\deg} followed by (100) with {\Theta} = 93.91{\deg}. The CeO2 (110) surface was, on the other hand, mildly hydrophilic with {\Theta} = 64.09{\deg}. By combining our calculations with an atomistic thermodynamic approach, we found that the O terminated (100) surface was unstable unless fully covered by molecularly adsorbed water. We also identified a strong attractive interaction between the hydrogen atoms in water molecules and surface oxygen, which gives rise to the hydrophilic behaviour of (110) surfaces. Interestingly, the adsorption of water molecules on the lower-energy (111) surface stabilises oxygen vacancies, which are expected to enhance the catalytic activity of this plane. The findings here shed light on the origin of the intrinsic wettability of rare earth oxides in general and CeO2 surfaces in particular and also explain why CeO2 (100) surface properties are so critically dependant on applied synthesis methods.

International audience; Fluid-filled porous materials are widely encountered in natural and artificial systems. A comprehensive understanding of the elastic behavior of such materials and its dependence on fluid diffusion is therefore of fundamental importance. In this work, a multiscale framework is developed to model the overall elastic response of fluid-filled porous materials. By utilizing a two-dimensional micromechanical model with porosity at two scales, the effects of fluid diffusion and the geometric arrangement of pores on the evolution of effective properties in fluid-filled porous materials are investigated. Initially, for a single-porosity model the effective elastic properties of the dry and fluid-filled porous materials with ordered pores are obtained theoretically by considering a geometrical factor, which is related to the distribution of pores in the matrix. Model predictions are validated by finite element simulations. By employing a double-porosity model, fluid diffusion from macro- to micro-scale pores driven by a pressure gradient is investigated, and the resulting time-dependent effective elastic properties are obtained for both constant pressure and constant injection rate conditions. It is found that the presence and diffusion of pressurized pore fluid significantly affect the elastic response of porous materials, and this must be considered when modeling such materials. It is expected that the proposed theoretical model will advance the understanding of the fluid-governed elastic response of porous materials with implications towards the analysis of geophysical, biological and artificial fluid-filled porous systems.https://doi.org/10.1016/j.ijsolstr.2018.11.028; Les matériaux poreux remplis de fluide sont largement rencontrés dans les systèmes naturels et artificiels. Une compréhension globale du comportement élastique de tels matériaux et de sa dépendance à la diffusion de fluide revêt donc une importance fondamentale. Dans ce travail, un cadre multi-échelles est développé pour modéliser la réponse élastique globale des matériaux poreux remplis de fluide. En utilisant un modèle micromécanique bidimensionnel avec une porosité à deux échelles, on étudie les effets de la diffusion de fluide et la disposition géométrique des pores sur l'évolution des propriétés effectives dans les matériaux poreux remplis de fluide. Initialement, pour un modèle à une seule porosité, les propriétés élastiques effectives des matériaux poreux secs et remplis de fluide à pores ordonnés sont obtenues théoriquement en considérant un facteur géométrique, qui est lié à la distribution des pores dans la matrice. Les prévisions du modèle sont validées par des simulations par éléments finis. En utilisant un modèle à double porosité, on étudie la diffusion de fluide à partir de pores de macro à micro échelle, entraînés par un gradient de pression, et on obtient les propriétés élastiques effectives dépendantes du temps qui en résultent, à la fois pour des conditions de pression constante et de vitesse d'injection constante. On constate que la présence et la diffusion de fluide interstitiel sous pression affectent de manière significative la réponse élastique des matériaux poreux, ce qui doit être pris en compte lors de la modélisation de tels matériaux. Le modèle théorique proposé devrait permettre de mieux comprendre la réponse élastique des matériaux poreux régie par les fluides, avec des implications pour l'analyse de systèmes poreux remplis de fluides géophysiques, biologiques et artificiels.

Composite materials comprising a porous Ti2AlC matrix and Al 6061 alloy were fabricated by a current-activated pressure assisted melt infiltration process. Coarse, medium and fine meso-structures were prepared with Al alloy filled pores of differing sizes. Materials were subjected to uniaxial compressive loading up to stresses of 668 MPa, leading to the failure of specimens through crack propagation in both phases. As-fabricated and post-failure specimens were analysed by X-ray microscopy and electron microscopy. Quasi-static mechanical testing results revealed that compressive strength was the highest in the fine structured composite materials. While the coarse structured specimens exhibited a compressive strength of 80% relative to this. Reconstructed micro-scale X-ray tomography data revealed different crack propagation mechanisms. Large planar shear cracks propagated throughout the fine structured materials while the coarser specimens exhibited networks of branching cracks propagating preferentially along Al alloy-Ti2AlC phase interfaces and through shrinkage pores in the Al alloy phase. Results suggest that control of porosity, compensation for Al alloy shrinkage and enhancement of the Al alloy-Ti2AlC phase interfaces are key considerations in the design of high performance metal/Ti2AlC phase composites., Comment: https://www.sciencedirect.com/science/article/pii/S0921509316307419

International audience; Copper dopants are varyingly reported to enhance photocatalytic activity at titanium dioxide surfaces through uncertain mechanisms. In order to interpret how copper doping might alter the performance of titanium dioxide photocatalysts in aqueous media we applied density functional theory methods to simulate surface units of doped anatase (101) planes. By including van der Waals interactions, we consider the energetics of adsorbed water at anatase surfaces in pristine and copper doped systems. Simulation results indicate that copper dopant at anatase (101) surfaces is most stable in a 2+ oxidation state and a disperse configuration, suggesting the formation of secondary CuO phases is energetically unfavourable. In agreement with previous reports, water at the studied surface is predicted to exhibit molecular adsorption with this tendency slightly enhanced by copper. Results imply that the enhancement of photoactivity at anatase surfaces through Cu doping is more likely to arise from electronic interactions mediated by charge transfer and inter-bandgap states increasing photoexcitation and extending surface-hole lifetimes rather than through the increased density of adsorbed hydroxyl groups.https://doi.org/10.1016/j.apsusc.2016.06.178; Il a été rapporté que les dopants au cuivre amélioraient l'activité photocatalytique à la surface du dioxyde de titane par le biais de mécanismes incertains. Afin d’interpréter la façon dont le dopage au cuivre pourrait altérer les performances des photocatalyseurs en dioxyde de titane en milieu aqueux, nous avons appliqué des méthodes de théorie de la densité fonctionnelle pour simuler des unités de surface de plans anatase (101) dopés. En incluant les interactions de van der Waals, nous considérons l’énergétique de l’eau adsorbée aux surfaces anatases dans les systèmes vierges et dopés au cuivre. Les résultats de la simulation indiquent que le dopant au cuivre à la surface de l'anatase (101) est le plus stable dans un état d'oxydation 2+ et dans une configuration dispersée, ce qui suggère que la formation de phases secondaires de CuO est énergétiquement défavorable. En accord avec les rapports précédents, il est prévu que l'eau présente à la surface étudiée présente une adsorption moléculaire avec cette tendance légèrement renforcée par le cuivre. Les résultats impliquent que l'amélioration de la photoactivité sur les surfaces de l'anatase par le dopage au Cu est plus susceptible de résulter d'interactions électroniques induites par le transfert de charge et les états inter-bandes interdites augmentant la photoexcitation et allongeant la durée de vie des trous de surface plutôt que par la densité accrue de groupes hydroxyles adsorbés.https://doi.org/10.1016/j.apsusc.2016.06.178

Effective thermal conductivity is an important property of granular materials in engineering applications and industrial processes, including the blending and mixing of powders, sintering of ceramics and refractory metals, and electrochemical interactions in fuel cells and Li-ion batteries. The thermo-mechanical properties of granular materials with macroscopic particle sizes (above 1 mm) have been investigated experimentally and theoretically, but knowledge remains limited for materials consisting of micro/nanosized grains. In this work we study the effective thermal conductivity of micro/nanopowders under varying conditions of mechanical stress and gas pressure via the discrete thermal resistance method. In this proposed method, a unit cell of contact structure is regarded as one thermal resistor. Thermal transport between two contacting particles and through the gas phase (including conduction in the gas phase and heat transfer of solid-gas interfaces) are the main mechanisms. Due to the small size of particles, the gas phase is limited to a small volume and a simplified gas heat transfer model is applied considering the Knudsen number. During loading, changes in the gas volume and the contact area between particles are simulated by the finite element method. The thermal resistance of one contact unit is calculated through the combination of the heat transfer mechanisms. A simplified relationship between effective thermal conductivity and loading pressure can be obtained by integrating the contact units of the compacted powders.

International audience; One of the many attributes of 3D printing is the ability to produce particles with independent control of morphology and material properties, parameters that are inexorably entwined in naturally occurring geomaterials. In this paper we describe the 3D printing of surrogate granular materials, show examples of the particles produced and present results showing their ability to capture real soil behaviour. Three approaches are demonstrated for the three dimensional generation of model grains. The first method involves the superimposition of a fractal surface with higher level stochastic features on the face of a closed volume such as a geodesic spheroid. The second method involves the use of Fourier descriptors or fractal geometry generated from 2D cross sections and their interpolation to produce simulated geomaterial particles in three dimensions. The third method involves the generation of complex particles by the aggregation of polyhedral elements such as cubes or octahedra which is suitable for the simulation and fabrication of porous or branching particles. Finally, we discuss applications of the fabrication of surrogate materials by 3D printing for use as standardised, printable geomaterials in future up-scaled geotechnical experiments and other geomechanical research.https://doi.org/10.1680/jgeot.15.P.034; L'un des nombreux attributs de l'impression 3D est la capacité de produire des particules avec un contrôle indépendant de la morphologie et des propriétés du matériau, paramètres inextricablement liés dans les géomatériaux naturels. Dans cet article, nous décrivons l'impression 3D de matériaux granulaires de substitution, montrons des exemples de particules produites et présentons les résultats montrant leur capacité à capturer le comportement réel du sol. Trois approches sont démontrées pour la génération tridimensionnelle de grains modèles. La première méthode implique la superposition d'une surface fractale avec des caractéristiques stochastiques de niveau supérieur sur la face d'un volume fermé tel qu'un sphéroïde géodésique. La deuxième méthode implique l'utilisation de descripteurs de Fourier ou de géométrie fractale générés à partir de sections transversales 2D et leur interpolation pour produire des particules de géomatériau simulées en trois dimensions. La troisième méthode implique la génération de particules complexes par l'agrégation d'éléments polyédriques, tels que des cubes ou des octaèdres, qui conviennent à la simulation et à la fabrication de particules poreuses ou ramifiées. Enfin, nous discutons des applications de la fabrication de matériaux de substitution par impression 3D pour une utilisation en tant que géomatériaux imprimables et normalisés dans de futures expériences géotechniques à grande échelle et autres recherches géomécaniques.https://doi.org/10.1680/jgeot.15.P.034

International audience; In this study, high-resolution transmission electron microscopy (HRTEM) was employed to characterize the nanostructure of strontium-substituted hydroxyapatite (Sr-HA) and its evolution following in vitro immersion in physiological solutions. HRTEM images showed that the substitution of Sr induced local distortions in the hydroxyapatite (HA) lattice: minor levels of edge dislocations were detected at low doping contents of Sr ions (1 at %); when the Sr content exceeded 10 at%, the density of grain boundaries increased notably and triple junctions were clearly observed. The dissolution of undoped HA was initiated at crystallite surfaces, whereas the dissolution of Sr-HA started around grain boundaries. Acicular nanocrystal reprecipitation was observed on grain surfaces immersed in simulated body fluid (SBF), while not in dilute hydrochloric acid (HCl). These findings suggest appropriate levels of Sr incorporation can introduce imperfections in the crystal structure of apatite and thus enhance its dissolution rate towards enhanced physicochemical performance in biomedical applicationshttps://doi.org/10.1016/j.jeurceramsoc.2018.07.056; Dans cette étude, la microscopie électronique à transmission à haute résolution (HRTEM) a été utilisée pour caractériser la nanostructure de l'hydroxyapatite substituée au strontium (Sr-HA) et son évolution après immersion in vitro dans des solutions physiologiques. Les images HRTEM ont montré que la substitution des distorsions locales induites par le Sr dans le réseau d'hydroxyapatite (HA): des niveaux mineurs de dislocations de bords ont été détectés à de faibles teneurs en dopage d'ions Sr (1 at%); lorsque la teneur en Sr dépassait 10% at%, la densité des joints de grains augmentait de manière notable et des triple jonctions étaient clairement observées. La dissolution de l'HA non dopée a été initiée au niveau des surfaces de cristallites, alors que la dissolution de Sr-HA a commencé autour des joints de grains. Une reprécipitation aciculaire de nanocristaux a été observée sur des surfaces de grains immergées dans un fluide corporel simulé (SBF), mais non dans de l'acide chlorhydrique dilué (HCl). Ces découvertes suggèrent que des niveaux appropriés d’incorporation de Sr peuvent introduire des imperfections dans la structure cristalline de l’apatite et ainsi augmenter sa vitesse de dissolution afin d’améliorer les performances physicochimiques dans les applications biomédicales.https://doi.org/10.1016/j.jeurceramsoc.2018.07.056

Structural characteristics are considered to be the dominant factors in determining the effective properties of granular media, particularly in the scope of transport phenomena. Towards improved heat management, thermal transport in granular media requires an improved fundamental understanding. In this study, the effects of packing structure on heat transfer in granular media are evaluated at macro- and grain-scales. At the grain-scale, a gas-solid coupling heat transfer model is adapted into a discrete-element-method to simulate this transport phenomenon. The numerical framework is validated by experimental data obtained using a plane source technique, and the Smoluschowski effect of the gas phase is found to be captured by this extension. By considering packings of spherical SiO2 grains with an interstitial helium phase, vibration induced ordering in granular media is studied, using the simulation methods developed here, to investigate how disorder-to-order transitions of packing structure enhance effective thermal conductivity. Grain-scale thermal transport is shown to be influenced by the local neighbourhood configuration of individual grains. The formation of an ordered packing structure enhances both global and local thermal transport. This study provides a structure approach to explain transport phenomena, which can be applied in properties modification for granular media., 11 figures, 29 pages

International audience; Capillary penetration of liquids in porous media is of great importance in many applications and the ability to tune such penetration processes is increasingly sought after. In general, liquid penetration can be retarded or restricted by the evaporation of volatile liquid at the surface of the porous media. Moreover, when capillary penetration occurs in a porous layer with non-uniform cross section, the penetration process can be accelerated or impeded by adjusting the section geometry. In this work, on the basis of Darcy's Law and mass conservation, a theoretical model of capillary penetration combining evaporation effects in two-dimensional homogeneous porous media of varying cross-section is developed and further examined by numerical simulations. The effects of sample geometry and liquid evaporation on capillary penetration are quantitatively analyzed. Results show that the penetration velocity is sensitive to the geometry of the porous layer, and can be tuned by varying the evaporation rate for a given geometry. Under given evaporation conditions, penetration is restricted to a limited region with a predictable boundary. Furthermore, we find that the inhibition of liquid penetration by evaporation can be offset by varying the geometry of the porous layer. In addition, the theoretical model is further extended to model the capillary flow in three-dimensional porous media, and the interplay of geometry and evaporation during the capillary flow process in 3D conditions is also investigated. The results obtained can be used for facilitating the design of porous structures, achieving tunable capillary penetration for practical applications in various fields.; La pénétration capillaire de liquides dans des milieux poreux revêt une grande importance dans de nombreuses applications et la capacité de réglage de tels processus de pénétration est de plus en plus recherchée. En général, la pénétration de liquide peut être retardée ou limitée par l'évaporation de liquide volatil à la surface du support poreux. De plus, lorsque la pénétration capillaire se produit dans une couche poreuse de section transversale non uniforme, le processus de pénétration peut être accéléré ou empêché en ajustant la géométrie de la section. Dans ce travail, sur la base de la loi de Darcy et de la conservation de masse, un modèle théorique de pénétration capillaire combinant les effets d'évaporation dans des milieux poreux homogènes à deux dimensions de sections différentes est développé et examiné plus en détail par des simulations numériques. Les effets de la géométrie de l'échantillon et de l'évaporation du liquide sur la pénétration capillaire sont analysés de manière quantitative. Les résultats montrent que la vitesse de pénétration est sensible à la géométrie de la couche poreuse et peut être ajustée en faisant varier le taux d'évaporation pour une géométrie donnée. Dans des conditions d'évaporation données, la pénétration est limitée à une région limitée avec une limite prévisible. En outre, nous trouvons que l'inhibition de la pénétration du liquide par évaporation peut être compensée en faisant varier la géométrie de la couche poreuse. En outre, le modèle théorique est élargi pour modéliser l'écoulement capillaire dans des milieux poreux tridimensionnels, et les interactions entre la géométrie et l'évaporation pendant le processus d'écoulement capillaire dans des conditions 3D sont également étudiées. Les résultats obtenus peuvent être utilisés pour faciliter la conception de structures poreuses, en réalisant une pénétration capillaire ajustable pour des applications pratiques dans divers domaines.

International audience; The Pechini method was more effective in fabricating Ce/Cr codoped TiO2 nanoparticles of superior photocatalytic properties in comparison with the sol-gel method. The improved efficiency was attributed to: a) formation of mixed-phase anatase + rutile with greater homogeneity of dopant incorporation, b) development of open agglomerated morphologies with significantly higher surface areas, and c) favourable valence changes (increased Ti 3+ concentrations) owing to electron exchange in inter valence and/or multi valence charge transfer reactions. Chen, Wen-Fan, et al. "Enhancement of Ce/Cr Codopant Solubility and Abstract Ce/Cr codoped TiO2 nanoparticles were synthesized using sol-gel and Pechini methods with heat treatment at 400°C for 4 h. A conventional sol-gel process produced well crystallized anatase while Pechini synthesis yielded less ordered mixed-phase anatase + rutile; this suggests that the latter method enhances Ce solubility, increases chemical homogeneity, but destabilizes the TiO2 lattice. Greater structural disruption from the decomposition of the Pechini precursor formed more open agglomerated morphologies while the lower levels of structural disruption from pyrolysis of the dried sol-gel precursor resulted in denser agglomerates of lower surface areas. Codoping and associated destabilization of the lattice reduced the binding energies in both powders. Cr 4+ formation in sol-gel powders and Cr 6+ formation in Pechini powders suggest that these valence changes derive from synergistic electron exchange from intervalence and/or multivalence charge transfer. Since Ce is too large to allow either substitutional or interstitial solid solubility, the concept of integrated solubility is introduced, in which the Ti site and an adjacent interstice are occupied by the large Ce ion. The photocatalytic performance data show that codoping was detrimental owing to the effects of reduced crystallinity from lattice destabilization and surface area. Two regimes of mechanistic behavior are seen, which are attributed to the unsaturated solid solutions at lower codopant levels and supersaturated solid solutions at higher levels. The present work demonstrates that the Pechini method offers a processing technique that is superior to sol-gel because the former facilitates solid solubility and consequent chemical homogeneity.

International audience; Granular crystallisation is an important phenomenon whereby ordered packing structures form in granular matter under vibration. However, compared with the well-developed principles of crystallisation at the atomic scale, crystallisation in granular matter remains relatively poorly understood. To investigate this behaviour further and bridge the fields of granular matter and materials science, we simulated mono-disperse spheres confined in cylindrical containers to study their structural dynamics during vibration. By applying adequate vibration, disorder-to-order transitions were induced. Such transitions were characterised at the particle scale through bond orientation order parameters. As a result, emergent crystallisation was indicated by the enhancement of the local order of individual particles and the number of ordered particles. The observed heterogeneous crystallisation was characterised by the evolution of the spatial distributions via coarse-graining the order index. Crystalline regimes epitaxially grew from templates formed near the container walls during vibration, here termed the wall effect. By varying the geometrical dimensions of cylindrical containers, the obtained crystallised structures were found to differ at the cylindrical wall zone and the planar bottom wall zone. The formed packing structures were quantitatively compared to X-ray tomography results using again these order parameters. The findings here provide a microscopic perspective for developing laws governing structural dynamics in granular matter.https://doi.org/10.1007/s10035-019-0876-8; La cristallisation granulaire est un phénomène important dans lequel des structures de garnissage ordonnées se forment dans une matière granulaire sous vibration. Cependant, comparée aux principes bien développés de la cristallisation à l'échelle atomique, la cristallisation dans la matière granulaire reste relativement mal comprise. Pour étudier plus avant ce comportement et relier les domaines de la matière granulaire et de la science des matériaux, nous avons simulé des sphères mono-dispersées confinées dans des conteneurs cylindriques afin d'étudier leur dynamique structurelle lors de la vibration. En appliquant une vibration adéquate, des transitions désordre à ordre ont été induites. Ces transitions ont été caractérisées à l'échelle des particules par le biais de paramètres d'ordre d'orientation de liaison. En conséquence, la cristallisation émergente était indiquée par l'amélioration de l'ordre local des particules individuelles et du nombre de particules ordonnées. La cristallisation hétérogène observée a été caractérisée par l'évolution des distributions spatiales via la granulation grossière de l'indice d'ordre. Les régimes cristallins se développaient par épitaxie à partir de gabarits formés près des parois du conteneur lors de vibrations, appelé ici effet de paroi. En faisant varier les dimensions géométriques des récipients cylindriques, il s'est avéré que les structures cristallisées obtenues différaient au niveau de la zone de paroi cylindrique et de la zone de paroi de fond plane. Les structures de garnissage formées ont été comparées quantitativement aux résultats de tomographie à rayons X en utilisant à nouveau ces paramètres d'ordre. Les résultats présentés ici fournissent une perspective microscopique pour l'élaboration de lois régissant la dynamique structurelle dans la matière granulaire.https://doi.org/10.1007/s10035-019-0876-8

The crumpling of precursor materials to form dense three dimensional geometries offers an attractive route towards the utilisation of minor-value waste materials. Crumple-forming results in a mesostructured system in which mechanical properties of the material are governed by complex cross-scale deformation mechanisms. Here we investigate the physical and mechanical properties of dense compacted structures fabricated by the confined uniaxial compression of a cellulose tissue to yield crumpled mesostructuring. A total of 25 specimens of various densities were tested under compression. Crumple formed specimens exhibited densities in the range 0.8–1.3 g cm−3, and showed high strength to weight characteristics, achieving ultimate compressive strength values of up to 200 MPa under both quasi-static and high strain rate loading conditions and deformation energy that compares well to engineering materials of similar density. The materials fabricated in this work and their mechanical attributes demonstrate the potential of crumple-forming approaches in the fabrication of novel energy-absorbing materials from low-cost precursors such as recycled paper. Stiffness and toughness of the materials exhibit density dependence suggesting this forming technique further allows controllable impact energy dissipation rates in dynamic applications.

The electrical contact resistance between contacting rough surfaces was studied under various compressive stresses. The samples considered here were isotropically roughened aluminium disks with upper and lower surfaces modified through polishing and sand blasting using different sized glass beads. Fractal geometry and roughness descriptors, including root mean square values of roughness and slope, were used to describe the topography of sample surfaces, based on the digitized profiles obtained from interferometry-based profilometry. The electrical contact resistances at the interfaces were obtained by applying a controlled current and measuring the resulting voltage, through the following scenarios: (1) over time for various applied testing currents, the resistance relaxation curves were measured at constant loads; (2) through voltage-current characteristics by means of a logarithmic sweeping current, the influence of the testing current on the electrical response of contacting rough surfaces was ...

In this paper we apply lattice models of finite binary percolation networks to examine the effects of network configuration on macroscopic network responses. We consider both square and rectangular lattice structures in which bonds between nodes are randomly assigned to be either resistors or capacitors. Results show that for given network geometries, the overall normalised frequency-dependent electrical conductivities for different capacitor proportions are found to converge at a characteristic frequency. Networks with sufficiently large size tend to share the same convergence point uninfluenced by the boundary and electrode conditions, can be then regarded as homogeneous media. For these networks, the span of the emergent scaling region is found to be primarily determined by the smaller network dimension (width or length). This study identifies the applicability of power-law scaling in random two phase systems of different topological configurations. This understanding has implications in the design and testing of disordered systems in diverse applications.

The hydro-mechanical behaviour of partially saturated granular materials is greatly influenced by the spatial and temporal distribution of liquid within the media. The aim of this paper is to characterise the distribution of saturated clusters in granular materials using an optical imaging method under different water drainage conditions. A saturated cluster is formed when a liquid phase fully occupies the pore space between solid grains in a localized region. The samples considered here were prepared by vibrating mono-sized glass beads to form closely packed assemblies in a rectangular container. A range of drainage conditions were applied to the specimen by tilting the container and employing different flow rates, and the liquid pressure was recorded at different positions in the experimental cell. The formation of saturated clusters during the liquid withdrawal processes is governed by three competing mechanisms arising from viscous, capillary, and gravitational forces. When the flow rate is sufficiently large and the gravity component is sufficiently small, the viscous force tends to destabilize the liquid front leading to the formation of narrow fingers of saturated material. As the water channels along these liquid fingers break, saturated clusters are formed inside the specimen. Subsequently, a spatial and temporal distribution of saturated clusters can be observed. We investigated the resulting saturated cluster distribution as a function of flow rate and gravity to achieve a fundamental understanding of the formation and evolution of such clusters in partially saturated granular materials. This study serves as a bridge between pore-scale behavior and the overall hydro-mechanical characteristics in partially saturated soils.

We experimentally and numerically examine stress-dependent electrical transport in granular materials to elucidate the origins of their universal dielectric response. The ac responses of granular systems under varied compressive loadings consistently exhibit a transition from a resistive plateau at low frequencies to a state of nearly constant loss at high frequencies. By using characteristic frequencies corresponding to the onset of conductance dispersion and measured direct-current resistance as scaling parameters to normalize the measured impedance, results of the spectra under different stress states collapse onto a single master curve, revealing well-defined stress-independent universality. In order to model this electrical transport, a contact network is constructed on the basis of prescribed packing structures, which is then used to establish a resistor-capacitor network by considering interactions between individual particles. In this model the frequency-dependent network response meaningfully reproduces the experimentally observed master curve exhibited by granular materials under various normal stress levels indicating this universal scaling behaviour is found to be governed by i) interfacial properties between grains and ii) the network configuration. The findings suggest the necessity of considering contact morphologies and packing structures in modelling electrical responses using network-based approaches., Comment: 12 pages, 4 figures

This work presents a combined experimental and theoretical study of dynamic contact angle hysteresis using liquid bridges under cyclic compression and stretching between two identical plates. Under various loading rates, contact angle hysteresis for three different liquids was measured by examination of advancing and receding angles in liquid bridges, and the capillary forces were recorded. It is found that, for a given liquid, the hysteretic phenomenon of the contact angle is more pronounced at higher loading rates. By unifying the behaviour of the three liquids, power-law correlations were proposed to describe the relationship between the dynamic contact angle and the capillary number for advancing and receding cases. It is found that the exponents of obtained power-law correlations differ from those derived through earlier methods (e.g., capillary rise), due to the different kinematics of the triple-line. The various hysteretic loops of capillary force in liquid bridges under varied cyclic loading rates were also observed, which can be captured quantitatively by the prediction of our developed model incorporating the dynamic contact angle hysteresis. These results illustrate the importance of varying triple-line geometries during dynamic wetting and dewetting processes, and warrant an improved modelling approach for higher level phenomena involving these processes, e.g., multiphase flow in porous media and liquid transfer between surfaces with moving contact lines., Comment: 24 pages, 6 figures

Using an organometallic precursor, TiO$_2$ coatings were fabricated on surfaces of quartz, zircon and rutile sands. X ray Diffraction, X ray Fluorescence, UV Vis spectroscopy and surface area measurement were used to characterise support materials. The phase composition and morphology of the coatings were characterised by laser Raman spectroscopy and SEM respectively. A packed bed reactor was used to study the inactivation of Escherichia coli in recirculating water by the supported photocatalysts. It was found that the sand grains were well coated with a homogenous layer of TiO2 and coatings were well adhered, exhibiting a mixed anatase rutile composition after firing at 850C. Photocatalytic activity was highest in coatings applied to quartz sand, although sterilisation of the recirculating water was not achieved with any of the materials investigated. The advantages of quartz as a TiO$_2$ photocatalyst support material are likely a result of this materials higher purity and optical transmittance. Potential enhancement through Si doping cannot be ruled out.

Responding to a lack in the literature, mechanical properties of polygonal wood particles are determined for use in a discrete element model (DEM) for flow analysis in silos, and some methods are proposed for determining such parameters. The parameters arrived at here have also formed part of the input to the SPOLY software, developed in-house to compute the DEM model with spheropolyhedron elements. The model is validated using a 2D physical model, where prismatic particles with polygonal cross sections are placed inside a silo with variable aperture and hopper angle. Validation includes comparison of flow-rates computed by SPOLY, displacement profiles, and clogging thresholds with experimental results. The good agreement that emerges will encourage future use of miniature triaxial tests, grain-surface profilometry, inclined slope tests, and numerical analysis of the intragranular stresses - toward a direct construction of the contact-deformation relations required in realistic DEM modelling of particle flow with angular-shaped particles.

Electrical networks of randomly distributed resistors, capacitors, and inductors have been observed to exhibit intrinsic electrical characteristics that show power law behavior with respect to the frequency of the electrical signal applied. To examine these scaling laws, we present an experimental investigation of the stress-dependent electrical properties of randomly packed spheres of stainless steel, subjected to various conditions of compressive force. We considered two types of spheres exhibiting different dimensions, in order to have different inter-particle forces, which govern interfacial electrical properties, at a given stress. The frequency-dependent conductance and impedance of packed beds are found to demonstrate power-law relationships within a certain range of frequency. The absolute value of the exponent of the observed power function varies with the applied stress. The capacitive-to-inductive phase transition was observed as load increased, and was found to depend on the applied stress level and surface-to-volume ratio. The approach of equivalent network circuit was developed to describe the variation of macroscopic impedance at various frequencies. This study provides an insight into the characteristic electrical behaviors of conductive granular materials.

The capillary penetration of fluids in thin porous layers is of fundamental interest in nature and various industrial applications. When capillary flows occur in porous media, the extent of penetration is known to increase with the square root of time following the Lucas-Washburn law. In practice, volatile liquid evaporates at the surface of porous media, which restricts penetration to a limited region. In this work, on the basis of Darcy's law and mass conservation, a general theoretical model is developed for the evaporation-limited radial capillary penetration in porous media. The presented model predicts that evaporation decreases the rate of fluid penetration and limits it to a critical radius. Furthermore, we construct a unified phase diagram that describes the limited penetration in an annular porous medium, in which the boundaries of outward and inward liquid are predicted quantitatively. It is expected that the proposed theoretical model will advance the understanding of penetration dynamics in porous media and facilitate the design of engineered porous architectures.

International audience; The effects of roughness and fractality on the normal contact stiffness of rough surfaces were investigated by considering samples of isotropically roughened aluminium. Surface features of samples were altered by polishing and by five surface mechanical treatments using different sized particles. Surface topology was characterised by interferometry-based profilometry and electron microscopy. Subsequently, the normal contact stiffness was evaluated through flat-tipped diamond nanoindentation tests employing the partial unloading method to isolate elastic deformation. Three indenter tips of various sizes were utilised in order to gain results across a wide range of stress levels. We focus on establishing relationships between interfacial stiffness and roughness descriptors, combined with the effects of the fractal dimension of surfaces over various length scales. The experimental results show that the observed contact stiffness is a power-law function of the normal force with the exponent of this relationship closely correlated to surfaces’ values of fractal dimension, yielding corresponding correlation coefficients above 90 %. A relatively weak correlation coefficient of 60 % was found between the exponent and surfaces’ RMS roughness values. The RMS roughness mainly contributes to the magnitude of the contact stiffness, when surfaces have similar fractal structures at a given loading, with a correlation coefficient of −95 %. These findings from this work can be served as the experimental basis for modelling contact stiffness on various rough surfaces.

International audience; In a range of energy systems, interfacial characteristics at the finest length scales strongly impact overall system performance, including cycle life, electrical power loss, and storage capacity. In this letter, we experimentally investigate the influence of surface topology on interfacial electro-mechanical properties, including contact stiffness and electrical conductance at rough surfaces under varying compressive stresses. We consider different rough surfaces modified through polishing and/or sand blasting. The measured normal contact stiffness, obtained through nanoindentation employing a partial unloading method, is shown to exhibit power law scaling with normal pressure, with the exponent of this relationship closely correlated to the fractal dimension of the surfaces. The electrical contact resistance at interfaces, measured using a controlled current method, revealed that the measured resistance is affected by testing current, mechanical loading, and surface topology. At a constant applied current, the electrical resistance as a function of applied normal stress is found to follow a power law within a certain range, the exponent of which is closely linked to surface topology. The correlation between stress-dependent electrical contact and normal contact stiffness is discussed based on simple scaling arguments. This study provides a first-order investigation connecting interfacial mechanical and electrical behaviour, applicable to studies of multiple components in energy systems.