We show that a nonlinear Schroedinger wave equation can reproduce all the features of linear quantum mechanics. This nonlinear wave equation is obtained by exploring, in a uniform language, the transition from fully classical theory governed by a nonlinear classical wave equation to quantum theory. The classical wave equation includes a nonlinear classicality enforcing potential which when eliminated transforms the wave equation into the linear Schro ̈dinger equation. We show that it is not necessary to completely cancel this nonlinearity to recover the linear behavior of quantum mechanics. Scaling the classicality enforcing potential is sufficient to have quantumlike features appear and is equivalent to scaling Planck’s constant.

We aim to describe a droplet bouncing on a vibrating bath using a simple and highly versatile model inspired from quantum mechanics. Close to the Faraday instability, a long-lived surface wave is created at each bounce, which serves as a pilot wave for the droplet. This leads to so called walking droplets or walkers. Since the seminal experiment by {\it Couder et al} [Phys. Rev. Lett. {\bf 97}, 154101 (2006)] there have been many attempts to accurately reproduce the experimental results. We propose to describe the trajectories of a walker using a Green function approach. The Green function is related to the Helmholtz equation with Neumann boundary conditions on the obstacle(s) and outgoing boundary conditions at infinity. For a single-slit geometry our model is exactly solvable and reproduces some general features observed experimentally. It stands for a promising candidate to account for the presence of arbitrary boundaries in the walker's dynamics.

(Graph Presented). In this study, we report the synthesis of Ti-doped mesoporous hematite films by soft-templating for application as photoanodes in the photoelectrolysis of water (water splitting). Because the activation of the dopant requires a heat treatment at high temperature (≥800°C), it usually results in the collapse of the mesostructure. We have overcome this obstacle by using a temporary SiO2 scaffold to hinder crystallite growth and thereby maintain the mesoporosity. The beneficial effect of the activated dopant has been confirmed by comparing the photocurrent of doped and undoped films treated at different temperatures. The role of the mesostructure was investigated by comparing dense, collapsed, and mesoporous films heated at different temperatures and characterized under front and back illumination. It turns out that the preservation of the mesotructure enables a better penetration of the electrolyte into the film and therefore reduces the distance that the photogenerated holes have to travel to reach the electrolyte. As a result, we found that mesoporous films with dopant activation at 850°C perform better than comparable dense and collapsed films.

Water-soluble star-like poly(vinyl alcohol)/C60 and poly{[poly(ethylene glycol) acrylate]-co- (vinyl acetate)}/C60 nanohybrids are prepared by grafting macroradicals onto C60 and are assessed as photosensitizers for photodynamic therapy. The photophysical and biological properties of both nanohybrids highlight key characteristics influencing their overall efficiency. The macromolecular structure (linear/graft) and nature (presence/absence of hydroxyl groups) of the polymeric arms respectively impact the photodynamic activity and the stealthiness of the nanohybrids. The advantages of both nanohybrids are encountered in a third one, poly[(Nvinylpyrrolidone)- co-(vinyl acetate)]/C60, which has linear grafts without hydroxyl groups, and shows a better photodynamic activity.

We experimentally investigate the effect of the grain shape on the flow of granular material. The grain shape is modified to highlight the effect of grain circularity on granular flow in a 2D rotating drum. Using a laser cutter, we create particles with decreasing circularity. We observe that the effect of grain shape depends on the rotation speed of the drum. For high rotation speed, granular flow is influenced by the packing’s dilatancy whereas, at low rotation speed, packing fraction seems to influence flowing dynamics. We link these two measurements to grain shape in order to explain its effect on granular flow.

For reaching high packing fractions, grains of various sizes are often mixed together allowing the small grains to fill the voids created by the large ones. However, in most cases, granular segregation occurs leading to lower packing fractions. We performed a wide set of experiments with different binary granular systems, proving that two main parameters are respectively the volume fraction f of small beads and the grain size ratio a. In addition, we show how granular segregation affects the global packing fraction. We propose a model with a strong dependency on a that takes into account possible granular segregation. Our model is in good agreement with both earlier experimental and simulation data.

For a few decades, the influence of a magnetic field on the aggregation process of superparamagnetic colloids has been well known on short time scale. However, the accurate study of the equilibrium state is still challenging on some aspects. On the numerical aspect, current simulations have only access to a restricted set of experimental conditions due to the computational cost of long-range interactions in many-body systems. In the present paper, we numerically explore a new range of parameters thanks to sped up numerical simulations validated by a recent experimental and numerical study. We first show that our simulations reproduce results from previous study in well-established conditions. Then we show that unexpectedly long chains are observed for higher volume fractions and intermediate fields. We also present theoretical developments taking into account the interaction between the chains which are able to reproduce the data that we obtained with our simulations. We finally confirm this model thanks to experimental data.

Once granular materials flow, particles charge because of the triboelectric effect. When particles touch each other, charges are exchanged during contact whether they are made of the same material or not. Surprisingly, when different sizes of particles are mixed together, large particles tend to charge positively while small particles charge negatively. If the particles are relatively small (typically smaller than a millimeter), the electrostatic interaction between the particles becomes significant and leads to aggregation or sticking on the surface of the container holding them. Studying those effects is challenging as the mechanisms that govern the triboelectric effect are not fully understood yet. We show that the patch model (or mosaic model) is suitable to reproduce numerically the flow of triboelectrically charged granular materials as the specific charging of bi-disperse granular materials can be retrieved. We investigate the influence of charging on the cohesion of granular materials and highlight the relevant parameters related to the patch model that influence cohesion. Our results shed new light on the mechanisms of the triboelectric effect as well as on how the charging of granular materials influences cohesion using numerical simulations.

The influence of a magnetic field on the aggregation process of superparamagnetic colloids has been well known on short time for a few decades. However, the influence of important parameters, such as viscosity of the liquid, has received only little attention. Moreover, the equilibrium state reached after a long time is still challenging on some aspects. Indeed, recent experimental measurements show deviations from pure analytical models in extreme conditions. Furthermore, current simulations would require several years of computing time to reach equilibrium state under those conditions. In the present paper, we show how viscosity influences the characteristic time of the aggregation process, with experimental measurements in agreement with previous theories on transient behaviour. Afterwards, we performed numerical simulations on equivalent systems with lower viscosities. Below a critical value of viscosity, a transition to a new aggregation regime is observed and analysed. We noticed this result can be used to reduce the numerical simulation time from several orders of magnitude, without modifying the intrinsic physical behaviour of the particles. However, it also implies that, for high magnetic fields, granular gases could have a very different behaviour from colloidal liquids.

We present a systematic experimental study of the confinement effect on the crystallization of a monolayer of magnetized beads. The particles are millimeter-scale grains interacting through the short range magnetic dipole-dipole potential induced by an external magnetic field. The grains are confined by repulsing walls and are homogeneously distributed inside the cell. A two-dimensional (2d) Brownian motion is induced by horizontal mechanical vibrations. Therefore, the balance between magnetic interaction and agitation allows investigating 2d phases through direct visualization. The effect of both confinement size and shape on the grains’ organization in the low-energy state has been investigated. Concerning the confinement shape, triangular, square, pentagonal, hexagonal, heptagonal, and circular geometries have been considered. The grain organization was analyzed after a slow cooling process. Through the measurement of the averaged bond order parameter for the different confinement geometries, it has been shown that cell geometry strongly affects the ordering of the system. Moreover, many kinds of defects, whose observation rate is linked to the geometry, have been observed: disclinations, dislocations, defects chain, and also more exotic defects such as a rosette. Finally, the influence of confinement size has been investigated and we point out that no finite-size effect occurs for a hexagonal cell, but the finite-size effect changes from one geometry to another.

Mixing particles of different sizes is an efficient method to increase the density of granular media. While the density of mixtures made of two sizes of glass beads has been highly studied, the dynamics of the compaction process remains poorly investigated. In our study, we measured the typical compaction time for various mixtures depending on the size ratio and the relative fraction of small and large beads. We observed a diverging behaviour of the compaction time close to the percolation threshold and we highlighted a fast compaction dynamics when the size ratio is large enough.

Targets were prepared to be used for magnetron sputtering and laser ablation and their microstructural and magnetic properties were investigated. The base material was nanosized MgFe2O4 powder produced by citrate auto-combustion synthesis. The auto-combusted powders were annealed at temperatures in the range 600 - 1000°C in air to study the effect of temperature on thofe formation MgFe2O4. The saturation magnetization Ms was 24.30 emu/g at room temperature. © Published under licence by IOP Publishing Ltd.

YBa2Cu3O7-δ thick films have been deposited onto Ag substrates by the Electrophoretic Deposition (EPD) technique. Different microstructures and electrical behaviours were observed depending on the starting powder. Coatings prepared from commercial powder displayed significant porosity and the superconducting transition width was found to be magnetic-field dependent. Films produced from home-made coprecipitated powder are denser but contain some secondary phases. No dependence of the resistive transition as a function of magnetic field (H ≤ 20 Oe) was observed in that case.

Doping at the Mn-site in CMR manganate-based perovskites has been shown to affect strongly the physical properties of those compounds. We study here the effect of copper substitution in the low doping range on the electrical transport properties of La0.7Ca0.3MnO3. It turns out that the transition temperature decrease observed in doped samples can be drastically reduced by addition of silicon dioxide SiO2. It is shown that copper is trapped in a secondary phase composed of La,Ca,Si,Cu and O. The resultant Mn-site vacancies appear to be less detrimental to the electronic conduction than the likely antiferromagnetic clusters induced by the copper ions in the Mn-O network.

We show that the synthesis conditions have a dramatic influence on the resistivity behavior of calcium and sodium doped LaMnO3. Several samples prepared by lowtemperature techniques exhibit a double-peaked curve of resistance versus temperature. The model of spin-polarized intergranular tunneling provides a good approach to discuss our experimental results. Grain size and crystallinity are proved to be essential parameters, which are strongly influenced by the preparation process (e.g. the precursors nature and the thermal treatment).

When placed onto a vibrating liquid bath, a droplet may adopt a permanent bouncing behavior, depending on both the forcing frequency and the forcing amplitude. The relationship between the droplet deformations and the bouncing mechanism is studied experimentally and theoretically through an asymmetric and dissipative bouncing spring model. Antiresonance phenomena are evidenced. Experiments and theoretical predictions show that both resonance at specific frequencies and antiresonance at Rayleigh frequencies play crucial roles in the bouncing mechanism. In particular, we show that they could be exploited for bouncing droplet size selection.

Antibubbles have been produced and studied with the help of a high-speed camera. An antibubble is defined as a fluid object constituted by a thin air shell surrounding a liquid and surrounded by the same liquid. Images reveal some key physical processes and fluid instabilities which take place when an antibubble forms and dies. The collapsing speed of the air film has been measured. Culik's theory does not apply. A new mechanism has been introduced.

We study the intermittent dynamics of collapsing foams. Avalanches of popping bubbles are observed. Although correlations between successive popping bubbles are emphasized, film raptures at the air/foam interface seem to be independent of the bubble size. Possible mechanisms for cascades of bubble pops are proposed and discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

We have experimentally studied the dense flow of identical bubbles below planes inclined at an angle theta. The flow is driven by the fast motion of dislocations. As a function of the density of dislocations (controlled by the parameter theta), a transition occurs between a simple collective block motion and a granular-like surface flow regime. (C) 2004 Elsevier B.V. All rights reserved.

We present an experimental study of the motion of a circular disk spun onto a table. With the help of a high speed video system, the temporal evolution of (i) the inclination angle alpha, (ii) the angular velocity omega, and (iii) the precession rate Omega are studied. The influence of the mass of the disk as well as the friction between the disk and the supporting surface are considered. Both inclination angle and angular velocity are observed to decrease according to a power law. We also show that the precession rate diverges as the motion stops. Measurements are performed very near the collapse as well as on long range times. Times to collapse have been also measured. Results are compared with previous theoretical and experimental works. The major source of energy dissipation is found to be the slipping of the disk on the plane.

We study the effect of freeze-thaw cycling on the packing fraction of equal spheres immersed in water. The water located between the grains experiences a dilatation during freezing and a contraction during melting. After several cycles, the packing fraction converges to a particular value η∞ = 0.595 independently of its initial value η0. This behavior is well reproduced by numerical simulations. Moreover, the numerical results allow one to analyze the packing structural configuration. With a Vorono ̈ı partition analysis, we show that the piles are fully random during the whole process and are characterized by two parameters: the average Vorono ̈ı volume μv (related to the packing fractionη)andthestandarddeviationσv ofVorono ̈ıvolumes.Thefreeze-thawdrivingmodifythevolumestandard deviation σv to converge to a particular disordered state with a packing fraction corresponding to the random loose packing fraction ηBRLP obtained by Bernal during his pioneering experimental work. Therefore, freeze-thaw cycling is found to be a soft and spatially homogeneous driving method for disordered granular materials.

We have experimentally investigated the interactions between floating magnetic spheres which are submitted to a vertical magnetic field, ensuring a tunable repulsion, while capillary forces induce attraction. We emphasize the complex arrangements of floating bodies. The equilibrium distance between particles exhibits hysteresis when the applied magnetic field is modified. Irreversible processes are evidenced. Symmetry breaking is also found for three identical floating bodies when the strength of the magnetic repulsion is tuned. We propose a Dejarguin-Landau-Verwey-Overbeek (DLVO)–like potential, i.e., an interaction potential with a primary and a secondary minimum, capturing the main physical features of the magnetocapillary interaction, which is relevant for self-assembly.

We investigate the stability of a granular monolayer composed of spherical grains on an inclined plate. When the tilt angle alpha increases, some reorganizations are observed throughout the pile. The packing fraction rho of the packing evolves by successive jumps. Those discontinuous events precede the collapse of the pile at a critical angle alphac. The occurrence of precursors before avalanches is modeled by stop-and-go motions of blocks due to the competition between sliding friction and the Janssen effect [J. Durand, (Springer-Verlag, New York, 2000)].

Charge carrier separation is considered as a key factor in enhancing the photocatalytic process and can be maximized by mitigating surface recombination. Following this idea, the surface of zinc oxide (ZnO) was modified by thermal treatment and nickel oxide (NiO) deposition. The influence of the ZnO thermal treatment and NiO deposition conditions on the ZnO surface chemistry and heterostructure interface properties were investigated by in situ X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) and correlated to the dye photodegradation efficiency. The XPS analysis confirmed a change of doping of ZnO after thermal treatment, which mainly influenced the developed band bending, and has led to an improved photocatalytic activity. For the same reason, the heterostructures based on the surface cleaned ZnO surface had higher photocatalytic efficiency than the ones based on non-cleaned ZnO. The temperature input during NiO deposition had negligible effect on the heterostructure interface properties. The photocatalytic efficiency did not follow the band bending evolution because of a dominant contribution of charge recombination across the NiO layer as indicated by PL analysis.

A key issue in the commercialization of dye-sensitized solar cells is to maintain high efficiency and long lifetime. As reported in the literature, dye-sensitized solar cells are stable under visible light soaking but thermal stress and UV exposure lead to efficiency degradation. However, all the stability studies published so far have been performed on cells whose TiO2 electrodes were prepared by tape casting or screen printing of nanoparticle pastes/inks. The present study concerns cells based on highly porous templated TiO2 electrodes, whose larger surface area could enhance the negative effects of thermal stress, light soaking and UV exposure. The long-term stability of these cells is compared with a classical nanoparticle-based cell using current-voltage measurements (I-V curves) and electrochemical impedance spectroscopy. Due to their higher active interface, templated cells are more sensitive than nanoparticle cells to UV illumination, although this can be easily solved in both cases by the use of a UV filter. The templated cells are as stable as the nanoparticle cells under visible light soaking (UV filtered). However, we showed that templated cells are more stable under thermal stress. Moreover, as evidenced by electrochemical impedance spectroscopy, templated cells show lower transfer resistance, as well as lower recombination resistance compared to nanoparticle cells. The crystallite connectivity promoted by the templating route seems to favor the electron transfers inside the porous layer. Using templated films in dye-sensitized solar cells is therefore really promising because higher conversion efficiencies are reached without promoting cell degradation.

In this study, we propose a straightforward method for x determination in sub-stoichiometric nickel oxide (Ni1−xO) films prepared by ultrasonic spray pyrolysis on fluor-tin oxide (FTO) substrates by varying the post-deposition thermal treatment. The Ni3+ concentration, the flat band potential (Φfb) and the open circuit potential (Voc) were determined by electrochemical impedance analysis in aqueous media and correlated to the transmission of Ni1−xO films. An x-ray photoelectron spectroscopy study was also performed to quantify the amount of Ni3+ in the films and compare it with the one determined by electrochemical analysis. The electrochromic behavior of the Ni1−xO films in non-aqueous electrolyte was investigated as well. With increasing Ni3+ concentration the films became more brownish and more conductive, both Voc and Φfb values increased. Calibration curves of transmission at 550 nm or open circuit potential versus carrier concentration were plotted and allowed the prediction of x in an unknown Ni1−xO sample. The Ni1−xO films characterized by the highest Ni3+ concentration have a darker colored state but lower transmission modulation, due to their reduced specific surface and increased crystallinity.

This paper offers an overview of the flow properties of granular systems, including voids, granular porosity and random packing characteristics. For the purposes of the study, the notion of additional porous volume is intro-duced. This volume is defined as the additional air volume added to the optimal granular packing. It represents the difference between the volume of the bulk powder bed and that of the same powder but when ideally packed. It appears as the volume of additional air (or voids) trapped/stored between the grains when the powder passes from a dynamical state to a static state (during the filling of a container or the formation of a powder heap, for example). Therefore, if the powder bed traps air, it is then able to restore air partially or completely or not at all, depending on the intergranular cohesion level. This mechanism of the storing and releasing of air can be analysed from the measurement of compressibility curves. If the powder is non-cohesive or free flowing, it traps a small amount of air in its static state. Conversely, if the powder is cohesive, it traps more air. These data can be related to the flow properties of granular materials. Indeed, the compressibility curves obtained for gran-ular materials provide information such as additional porosity, a kinetic parameter which characterizes the com-pressibility dynamics, a granular relaxation index which predicts how far a powder is from its optimal packing state and an index which gauges the de-areation speed of the powder. Measurement of such properties provides a better understanding of the nature of granular materials. Measurements of dynamical compressibility were car-ried out on five granular materials (two different lactose powders, hydrated lime Ca(OH)2, yttrium stabilized zir-conia balls and polystyrene balls). The overall results are presented using a radar graph. The use of this tool and its advantages are discussed in relation to the measurement and characterization of powder flow properties.

A granular material is a complex system which exhibits non-trivial transitions between the static, the quasi-static and the dynamical states. Indeed, an assembly of grains can behave like a solid or a fluid according to the applied stress. In between solid and fluid granular states, very slow dynamics are observed. When a complete macroscopic characterization of a powder is needed, all these granular states have to be precisely analyzed. In this paper, we show how three measurement techniques can be used to measure the physical properties of a powder. The measurements are based on classical tests modified to meet the recent fundamental researches on granular materials. The static properties of the powder are analyzed through the shape of a heap. The quasi-static behavior is studied with the analysis of the compaction dynamics. Finally, the dynamical regime is monitored through the flow in a rotating drum. In order to illustrate how these measurements can be used in practical cases, analyses are performed with three types of granular materials: silicon carbide abrasives, flours and rice. These selected materials allow to show the influence of the different parameters (grain size, grain size distribution, grain shape) on the macroscopic properties of the assembly. Moreover, these studies show the pertinence of the parameters obtained with the proposed techniques for the rheological characterization of powders and grains.

The density functional theory (DFT) computation of electronic structure, total energy and other properties of materials, is a field in constant progress. In order to stay at the forefront of knowledge, a DFT software project can benefit enormously from widespread collaboration, if handled properly. Also, modern software engineering concepts can considerably ease its development. The ABINIT project relies upon these ideas: freedom of sources, reliability, portability, and self-documentation are emphasised, in the development of a sophisticated plane-wave pseudopotential code. We describe ABINITv3.0, distributed under the GNU General Public License. The list of ABINITv3.0 capabilities is presented, as well as the different software techniques that have been used until now: PERL scripts and CPP directives treat a unique set of FORTRAN90 source files to generate sequential (or parallel) object code for many different platforms; more than 200 automated tests secure existing capabilities; strict coding rules are followed; the documentation is extensive, including online help files, tutorials, and HTML-formatted sources. (C) 2002 Elsevier Science B.V. All rights reserved.

This study quantifies the highest perturbation encountered by the first layer of a TiO2 12 layers-mesoporous coating, which is submitted to a multistep calcination process. Besides, we propose an alternative thermal treatment in order to limit the degradation induced by repeated calcinations. This paper reports and compares the modifications in film thickness, surface area, anatase crystallite size and global crystallinity of films obtained from different thermal treatments. It defines the maximum crystal size compatible with the preservation of the mesoarchitecture initially induced by templating. Differences in microporosity and rate of crystallization are also discussed.

Due to their large surface-area-to-volume ratio as well as their interesting intrinsic optical and electronic properties, ZnO 1D nanostructures are part of the few dominant materials for nanotechnology. In this article, we compare two different routes of using the nanosphere lithography for the manufacturing of well-aligned, density-controlled ZnO nanowires by low-temperature hydrothermal growth. The first route uses the colloidal mask as a template for the patterned growth of the nanowires, while in the second route, the nanospheres act as a mask to pattern the seed layer. SEM and XRD characterizations are performed on samples manufactured by both routes and evidence patterned well-aligned nanowires with high c-axis texturing in the first synthetic route. Oriented growth is less pronounced in the second route, as well as the ability to adsorb dye. However, for the first route the dye loading measurements reveal that the amount of N-719 adsorbed is higher than on unpatterned ZnO nanowires films, highlighting an increased interface area. Reversible hydrophobicity to superhydrophilicity transition was observed and intelligently controlled by alternation of UV illumination and dark storage. This promising synthetic route opens exciting perspectives for the production of ZnO nanowire arrays with tunable density, wetting properties and enhanced adsorption properties.

Multilayered YBa2Cu3O7-δ (YBCO) thick films were coated on silver substrates by electrophoretic deposition (EPD) followed by heat treatment. A butanol-based YBCO suspension is used instead of the common acetone-iodine combination. Tests with several dispersing agents reveal that a branched polyethyleneimine (PEI) dispersant develops large positive surface charge on suspended YBCO particles. As a demonstration of the performance of this new suspension formulation, a 12-layer 100 μm-thick YBCO coating was deposited on an Ag tube. The superconducting transition is sharp with onset critical temperature at 92 K. The sample can shield a magnetic field of ~1.3 mT at 77 K, i.e., the best value so far for an YBCO coating on a metallic substrate. © 2013 Elsevier B.V.

This paper presents the sintering behaviour of a La0.9Sr0.1Ga0.8Mg0.2O2.85 coral-like microstructure powder. This is prepared by a successive freeze-drying and self-ignition process followed by calcination at 1200 ◦C during 1 h. This synthesis method gives great uniformity of the powder and allows shaping into compacts without requiring a grinding step. The grain size distribution (between 0.5 and 4 m) favours a good sintering behaviour: open porosity disappear at 1400 ◦C and relative densities over 99% can be achieved after 6 h at 1450 ◦C. The same powder can also be sintered into a thin disc of ∼100 mthickness. The characterization of the dense material by impedance spectroscopy shows that the activation energies below and above 600 ◦C are 1.0 eV and 0.7 eV, respectively. The conductivity at 800 ◦C is ∼0.11 S cm−1. Special attention is devoted to the temperature range between 200 ◦C and 400 ◦C, where the intragrain and intergrain contributions can be distinguished. The analysis of the parameters describing the intragrain constant phase element in the equivalent circuit suggests that, above 325 ◦C, the system evolves from a distribution of relaxation time to only one relaxation time. The analysis of the data by the complexes permittivity show that ionic oxide conduction mechanism would occur in two steps. In the first, an oxygen vacancy would be released and, in the second, the migration of the ionic oxide would take place in the material.

The present paper reports the synthesis of La0.9Sr0.1Ga0.8Mg0.2O2.85 perovskite powders by a method combining freeze-drying and self-ignition of an aqueous solution of metallic nitrates containing hydroxypropylmethyl cellulose. The precursor powder obtained after self-ignition was submitted to various thermal treatments and the resulting powders were characterized by X-ray diffraction, electron microscopy, nitrogen adsorption-desorption isotherm analysis, mercury porosimetry and laser granulometry. It turns out that this synthesis method yields single-phase powders with good homogeneity and sinterability properties. The precursor powder treated at 1200 degrees C presents a coral-like structure which collapses under application of low uniaxial pressure, resulting in a narrow grain size distribution suitable for sintering (98.8% relative density for a pellet sintered at 1400 degrees C during 1 h). The fact that no milling step is necessary is an additional advantage of this method, which shows promising prospects for the synthesis of other multicationic oxides. (c) 2007 Elsevier Ltd. All rights reserved.

Synthesis of polycationic compounds by the spray-drying technique is an interesting alternative in the domain of aqueous precursor synthesis methods. Spray drying yields high quality samples with good reproducibility. The possibility of scaling up for production of large quantities with fast processing time is well established by the commercial availability of powders of various compositions. In this paper, we have discussed the advantages and limitations of this method and demonstrated its interest by synthesizing a few polycationic compounds selected for their attractive properties of thermoelectricity [Bi1.68Ca2Co1.69O8, La(0.95)A(0.05)CoO(3) (A = Ca, Sr, Ba)] or magnetoresistance [La(0.70)A(0.30)MnO(3) (A=Sr, Ba)]. We have confirmed the quality of these samples by reporting their structure, magnetic and transport properties. (C) 2010 Elsevier Ltd. All rights reserved.

Synthetic lamellar silica and hybrid lamellar silicas have been prepared by liquid crystal templating, template extraction and silanization. The samples have been characterized by thermogravimetric analysis (TGA), carbon analysis, spectroscopy, X-ray diffraction (XRD) and nitrogen adsorption. The XRD analyses have shown that the lamellar periodic stacking is preserved for all samples. The quantity and type of organic molecules at the silica surface have been evaluated by carbon analysis, TGA and spectroscopy. The covalent grafting of the solvent used for extraction of the initial surfactant has been highlighted by these analyses. The nitrogen adsorption analyses have revealed three categories of pores and two types of samples. The initial lamellar silica exhibits a very low specific surface area and plate-like type of pores. The second type of samples is made up of the hybrid samples and the initial substrate from whom the surfactant has been extracted. These samples show a significantly higher specific surface area with interlamellar spaces corresponding to narrow-slit like mesopores around 4 nm. The nitrogen adsorption data analysis has highlighted the presence of micropores within the silica sheets. The difference of the specific surface is due to pore blocking by the surfactant impeding the access to nitrogen into interlamellar spaces and by the silanes covering the pores once the surface modified. The presence of micro and mesopores combined to a high BET specific surface of 612 m²/g makes these lamellar silicas interesting materials for catalysis applications.

Barium hexaferrite powders of nanometer particle size synthesized via two variants of the microemulsion technique, namely, single microemulsion and double microemulsion, were studied. The influence was explored of the type of microemulsion technique on the microstructure and on the magnetic properties of the barium hexaferrite powders. The average particle size of the barium hexaferrite powders was in the range from 110 nm to 442 nm depending on the method and conditions of synthesis. The particles with size below 150 nm had irregular shapes between spherical and platehexagonal; the bigger ones had an almost perfect hexagonal shape. The powders obtained by single microemulsion had better magnetic characteristics (saturation magnetization of 65.12 emu/g and coercivity field of 3.6 × 105 A/m) than those obtained by double microemulsion. © 2013 Elsevier B.V. All rights reserved.

This work investigates the possibility to prepare mesoporous thin films of Li-Ti, Li-Nb, Li-Nb-V and Li-V oxides through a direct sol-gel EISA route by dissolving a lithium salt in the precursor solution. Experimental conditions involve a hydrolysis molar ratio H2O/TM ~10 (TM = Ti,Nb,V) and the common Pluronic structuring agent P123 (EO20-PO70-EO20). Systematic formation of lithium-containing oxides as first-crystallizing phases points to a significant intermixture of lithium and transition metal ions in the inorganic network. In the case of Ti-based and Nb-based oxide films, addition of lithium to the precursor solution is compatible with the formation of amorphous mesoporous films at 350°C. On the contrary, addition of lithium has a detrimental effect on the notoriously difficult formation of vanadium-based mesostructured films: even when replacing half of the vanadium by niobium as a stabilizer, formation of mesostructured films has not been possible in the investigated range of experimental conditions.

We report the high temperature thermoelectric properties of Ca1-xDyxMn1-yNbyO3-delta (x = 0, 0.02, 0.1 and y = 0, 0.02) synthesized by spray-drying method. A maximum power factor (PF) value of 2.65 mu WK-2 cm(-1) is obtained at 1100 K for CaMn0.98Nb0.02O3-delta. This represents an improvement of about 75% with respect to undoped CaMnO3-delta sample at the same temperature. We also provide a complete structural characterization of the samples. (C) 2011 Elsevier B.V. All rights reserved.

[Bi1.68Ca2O4](RS)[CoO2](1.69) (BCCO) sample and Ag-BCCO composites (with 10, 20 or 30 wt% Ag) have been prepared by the spray-drying technique and uniaxially/isostatically packed. Scanning electron microscopy reveals that the Ag particles are well distributed in the BCCO cobaltite matrix at low Ag contents. The Ag particles have an important effect on densification and grain orientation of the samples, with a direct impact on their electrical conductivity. The electrical conductivity is higher for the uniaxial samples and increases with the Ag content up to 20% in weight, while the Seebeck coefficient is hardly affected. These features induce an improvement of the power factor, reaching a maximum value of 2.2 mu W K-2 cm(-1) at similar to 1050 K for the uniaxial sample with 20 wt% Ag. Our results suggest that the spray-drying technique is a promising method to obtain composites with a well-dispersed secondary phase. (C) 2010 Elsevier Masson SAS. All rights reserved.

This paper is focused on the preparation and characterization of different lamellar silica prepared by liquid crystal templating and silanisation. The initial template can be removed and replaced in the interlamellar spaces by different types of silane, being covalently grafted to the solid by reaction with the surface silanols. The lamellar stacking periodicity remains after this modification. The surfactant extraction can lead in significant grafting of isopropanol if the solid is simply refluxed in isopropanol, which have the effect of preserving the periodicity of the lamellar stacking. The surfactant extraction in an Soxhlet equipment avoid this reaction, with the effect of platelets organization collapsing. The lamellar silica studied exhibit great specific surface and combination of meso and microporosity, making them interesting materials for nanocomposite or catalysis applications.

Lithium-doped nickel oxide and undoped nickel oxide thin films have been deposited on FTO/glass substrates by a surfactant-assisted ultrasonic spray pyrolysis. The addition of polyethylene glycol in the sprayed solution has led to improved uniformity and reduced light scattering compared to films made without surfactant. Furthermore, the presence of lithium ions in NiO films has resulted in improved electrochromic performances (coloration contrast and efficiency), but with a slight decrease of the electrochromic switching kinetics.

[Bi1 68Ca2O4 delta](RS)[CoO2](1 69) has been obtained by different chimie douce methods and uniaxially or isostatically pressed The influence of these parameters on the thermoelectric properties has been investigated. Contrary to the Seebeck coefficient, which remains unchanged, the electrical conductivity is greatly modified In particular, spray-drying synthesis followed by uniaxial pressing results in an electrical conductivity two times larger than in the case of conventional solid state synthesis. Our results suggest that a narrow particle size distribution is beneficial to the thermoelectric properties of the layered compounds. The spray-drying technique seems to be promising to Improve the electrical conductivity of layered materials. Moreover, this method presents other advantages (homogeneous samples and less energetic processing) which could be interesting to the future manufacturing of thermoelectric devices (C) 2010 Elsevier Inc. All rights reserved

The light scattering method has been adapted in dye-sensitized solar cells (DSCs) for optical absorption enhancement. In DSC's, particle-size of TiO2 should be inline with the scattering wavelength range. Scattering particles can be used either by forming a bilayer structure with TiO2 nanocrystalline film or into the bulk of TiO2 nanocrystalline film. For improving the DSCs performances these scattering layers aim to refract/reflect the incident light by extending the traveling distance of UV-Visible/near-IR light within the dye-sensitized TiO2 nanocrystalline film. In this work, the scattering layers with two different particle-sizes (~200 nm-solid and ~400 nm-hollow) were deposited as an additional layer on the top of dye-sensitized TiO2 nanocrystalline film and the morphological properties were studied. By using various opto-electrical characterization techniques, the influence of these scattering layers for two different classes of DSCs prepared from N3 (UV-Vis) and SQ2 (near-IR) dyes were investigated.

Yttrium orthoferrite (YFeO3) is a promising material for visible light photocatalytic applications due to its band gap of 2.2-2.6 eV. However, during the synthesis of YFeO3, unwanted composition can be obtained and the crystallization requires temperatures as high as 850 C. Powders of YFeO3 were prepared using a sol-gel method with and without organic acids (citric acid, tartaric acid, malonic acid and oxalic acid) used as organic modifiers. The band gap of these powders was measured by diffuse reflection spectroscopy, and the crystallinity and crystalline phase content were characterized by X-ray diffraction. Organic acids allow a higher purity and facilitate crystallization. This work aims to produce YFeO3 powders at the lowest possible temperature. Citric acid was found to be the best additive: it reduces the crystallization temperature below 450 C. This opens new perspectives such as the deposition of crystalline YFeO3 thin films onto conductive glass for water-splitting applications. © 2013 Elsevier B.V.

The chemical interactions between Bi2Sr3CaO7 (Bi-2310) and Bi2Sr2Ca0.8Dy0.2Cu2O8 (Bi-2212(Dy)) at 965 degrees C were investigated by means of: (i) an interdiffusion couple and (ii) layers deposited by dip coating on oxidized nickel Substrates. The samples were characterized by optical and electron microscopies, energy-dispersive x-ray (EDX) analysis and x-ray diffraction. It turns out that at the peritectic temperature Of Bi-2212(Dy), the Bi-2310 phase reacts with the liquid phase resulting from the peritectic decomposition of the Bi-2212(Dy) phase. Dissolution of Bi-2310 leads to an enrichment in Sr and an impoverishment in Cu of the liquid phase, resulting in a shift of the composition of the insoluble phase towards the Ca-rich end of the (Ca, Sr)O Solid Solution.

YBa2Cu3O7-delta coatings were deposited by electrophoretic deposition (EPD) onto Ni substrates. Particles of different sizes and shapes were used in order to study the influence of the powder microstructure on the film density. Texturation of the thick films was induced by application of a magnetic field during the electrophoretic deposition. X-ray diffraction analysis has clearly shown preferred c-axis alignment of the YBa2Cu3O7-delta films along the direction normal to the substrate surface. Scanning electron microscopy and optical polarised light microscopy were used to characterise the microstructure of the coatings, revealing a nonrandom platelets organisation.

We present the structural and magnetic properties of a multiferroic Ba2Mg2Fe12O22 hexaferrite composite containing a small amount of MgFe2O4. The composite material was obtained by auto-combustion synthesis and, alternatively, by co-precipitation. The Ba2Mg2Fe12O22 particles obtained by co-precipitation have an almost perfect hexagonal shape in contrast with those prepared by auto-combustion. Two magnetic phase transitions, responsible for the composite’s multiferroic properties, were observed, namely, at 183 K and 40 K for the material produced by auto-combustion, and at 196 K and 30 K for the sample prepared by co-precipitation. No magnetic phase transitions in these temperature ranges were observed for a MgFe2O4 sample, which shows that the magnesium ferrite does not affect the multiferroic properties of this type of multiferroic metarials.

Research in the field of lithium-ion batteries favours electrode materials with high surface area. In this context, this paper is dedicated to mesoporous thin films (MTFs) and compares the electrochemical performance of g-LiV2O5 MTFs with post-synthesis electrochemical lithium intercalation in a-V2O5 MTFs. Formation of vanadium oxide MTFs by soft-chemistry is notoriously difficult. However, it is shown that wormlike vanadium oxide (V–O) and lithium vanadium oxide (Li–V–O) MTFs can be obtained on silicon substrates by a direct sol–gel soft-templating route (evaporation-induced micelle assembly) using a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) structuring agent. Heat treatment for 1 minute at 400 C (Li–V–O system) or 30 minutes at 350 C (V–O system) leads to the crystallization of g-LiV2O5 or a-V2O5, respectively. These calcination conditions ensure the degradation of the structuring agent while preventing the collapse of the mesostructure, yielding MTFs with pore size diameter in the 30–35 nm range. Using the same set of synthesis conditions, films can be deposited on conductive glass substrates for electrochemical investigation: the a-V2O5 films display better specific capacities, while the cyclability is good for both compositions, even at a current density as high as 30 C-rate.

In this paper we report about the electrical properties of La0.7Ca0.3MnO3 compounds substituted by copper on the manganese site and/or deliberately contaminated by SiO2 in the reactant mixture. Several phenomena have been observed and discussed. SiO2 addition leads to the formation of an apatite-like secondary phase that affects the electrical conduction through the percolation of the charge carriers. On the other hand, depending on the relative amounts of copper and silicon, the temperature dependence of the electrical resistivity can be noticeably modified: our results enable us to compare the effects of crystallographic vacancies on the A and B sites of the perovskite with the influence of the copper ions substituted on the manganese site. The most original result occurs for the compounds with a small ratio Si/Cu, which display double-peaked resistivity vs. temperature curves. (C) 2003 Elsevier B.V. All rights reserved.

We have studied the electrical transport properties of manganate samples synthesized by different precursor methods. Differences in the synthesis process of the materials can result in samples with similar grain size but very different physical properties, contrary to what happens in samples prepared by the same method. (C) 2002 Elsevier Science B.V. All rights reserved.

Temperature influences drastically the physical properties of polymer powders. In the present study, the packing dynamics of polymer powders has been investigated with a modified version of GranuPack instrument, which is an improvement of the classical tapped density measurement. After the filling pro- cedure, the sample is heated and the evolution of the density is measured after each tap. For a selection of four polymers (polyamide 12, Polystyrene, Polyvinyl chloride and a thermoplastic polyurethane), the influence of temperature on the Hausner ratio and on the packing dynamics are analysed. We show that the packing dynamics is drastically influenced by temperature even far below the melting temperature Tm for semi-crystalline polymers and far below the glass-transition temperatures Tg for amorphous poly- mers. In addition, we show that the analysis of the packing dynamics at different temperatures allows to determine a characteristic temperature corresponding to the onset of caking. Finally, we show that this temperature is coherent with Differential Scanning Calorimetry (DSC) analysis.

Ethylene−vinyl alcohol copolymers (EVOHs) are important materials available in a variety of compositions and valued in countless applications. In spite of their great adaptability offered by the adjustment of their ethylene content, the chemical modification ofEVOHs is often considered to tune their properties and functionalities in order to meet the stringent requirements of today’s applications. While post-polymerization modification of the pendant hydroxyl groups of EVOHs is the prevailing functionaliz- ing strategy, this multistep approach consumes part of the alcohols of EVOHs and remains limited in terms of functions. This work reports a straightforward platform for the synthesis of functional EVOHs, in particular, amino derivatives, involving a CO2-derived oxazolidinone-containing methylene heterocycle, namely, 4,4-dimethyl-5-methyleneoxazolidin-2-one (DMOx). The ethylene/ DMOx and ethylene/vinyl acetate/DMOx copolymerizations were implemented by conventional and reversible deactivation radical copolymerization. The resulting oxazolidinone-containing ethylene-based copolymers were then converted into novel vicinal amino alcohol-functional EVOHs via hydrolysis of esters and oxazolidinones. A selective post-modification method of these 1,2-amino alcohol-functional EVOHs into their oxazolidine counterparts is also reported. Finally, the peculiar thermal and solution properties, including pH-responsiveness, of these novel vicinal amino alcohol- and oxazolidine-functional EVOHs as well as oxazolidinone EVAs are discussed.

The controlled radical copolymerization of ethylene (E) and vinyl acetate (VAc) is further investigated by organometallic- mediated radical polymerization (OMRP) using Co(acac)2 as controlling agent at ethylene pressure up to 100 bar. The effect of ethylene pressure on kinetics, level of control and copolymer composition, is discussed. Ethylene-Vinyl Acetate copolymers (EVAs) with low dispersities and ethylene content reaching 57 mol% are notably reported. This work also successfully addresses the precision design of EVA-containing block copolymers, i.e. PVAc-block-EVA. In this case, the order of the synthesis of the blocks is a key parameter. The “PVAc-first” strategy is by far more practical and efficient.

Considerable progress has been recently made in cobalt-mediated radical polymerization (CMRP), a controlled radical polymerization system based on the temporary deactivation of the polymer chains by a cobalt complex, like the improvement of the mechanistic understanding, the extension to a range of monomers and the preparation of novel architectures. However, the real breakthrough in this field concerns the development of efficient radical coupling methods for polymer precursors preformed by CMRP. This book chapter aims to describe the general principle and main characteristics of such radical coupling techniques involving dienes, nitrones, fullerenes or carbon nanotubes. Well-defined and complex architectures obtained by these techniques are provided in order to illustrate their potential for macromolecular engineering.

Cobalt mediated radical polymerization (CMRP) of vinyl acetate (VAc) follows a reversible termination mechanism when initiated from a preformed alkyl-cobalt(III) complex. In these particular conditions, CMRP functions as a stable free radical process and fine tuning of the Co-C bond strength becomes crucial. Increase of temperature and addition of molecules, such as water, dimethylformamide and dimethylsulfoxide, able to coordinate the cobalt complex appeared as efficient strategies to weaken the Co-C bond and thus to speed up the polymerization while maintaining a very good control of the VAc polymerization. The key role of metal-coordination was investigated by kinetic measurements combined with DFT calculations.

Poly(ethylene oxide)-b-polyphosphoester amphiphilic block copolymers are known to self-assemble into polymer micelles when dissolved into water. This work aims at reporting on the improvement of the stability of the micelles at high dilution by crosslinking the hydrophobic polyphosphoester micellar core. Typically, an unsaturated alkene side-chain was introduced on the cyclic phosphate monomer according to a one-step reaction followed by its organocatalyzed polymerization initiated by a poly(ethylene oxide) macroinitiator. This strategy avoids the use of any organometallic compounds in order to facilitate the purification and meet the stringent requirements of biomedical applications. After self-assembly into water, the micelles were cross-linked by simple UV irradiation. These cross-linked micelles have then been loaded by doxorubicin to evaluate their potential as drug nanocarriers and monitor the impact of crosslinking on the release profile.

The performances of titanium dioxide (TiO2) thin films used in photoelectrochemical applications (solar cells, water splitting, photocatalysis, etc) highly depend on their morphology and interface. In this work, we describe a straightforward strategy for designing conductive carbon-coated TiO2 porous layers allowing for the tuning of interfacial charge transfers. Increased specific surface and improved conductivity are expected from the porosity and the carbon coating, respectively. In practice, polystyrene/polyacrylonitrile (PS-PAN) and polystyrene/polydopamine (PS-PDA) core-shell particles synthesized by emulsion polymerization are considered as templating agents for the production of carbon-coated and ordered porous TiO2 layers. After spin coating deposition of the particles, infiltration of the TiO2 precursor and calcination, voids are created in the film by thermal degradation of the PS cores whereas PAN and PDA produced carbon at the surface of the TiO2 inverse opal matrix. Uncoated PS particles are also considered as benchmark templating agents. Size and composition of the polymer particles as well as the morphology and electronic properties of the corresponding porous TiO2 films are evaluated. In particular, the charge transfer resistance of the films is investigated via Electrochemical Impedance Spectroscopy (EIS) as a preliminary assessment of these unprecedented carbon-coated porous TiO2 layers as semiconducting materials

The modification of aliphatic polyesters by the copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) was successfully implemented in supercritical carbon dioxide (scCO2). Due to the remarkable properties of scCO2, the CuAAC reaction turned out to be quantitative even though the aliphatic polyesters used in this work were insoluble in scCO2. Interestingly enough, the conditions were mild enough to prevent polymer degradation from occurring and finally, efficient removal of the catalyst (>96%) was achieved by scCO2 extraction.

We report on the original synthesis of a poly(methacrylamide) bearing (oxidized) 3,4-dihydroxyphenylalanine specially designed to (i) insure film growth by covalent coupling, (ii) covalently bind an antibacterial peptide and (iii) contribute to the film cross-linking that is essential for the durability of the properties.

The Michael-type addition of aliphatic (co)polyesters onto gamma-acryloyloxy epsilon-caprolactone units is a very straightforward technique of functionalization and grafting, which is tolerant to a variety of functional groups and does not require intermediate protection/deprotection steps.

The performance of lithium‐ and sodium‐ion batteries relies notably on the accessibility to carbon electrodes of controllable porous structure and chemical composition. This work reports a facile synthesis of well‐defined N‐doped porous carbons (NPCs) using a poly(ionic liquid) (PIL) as precursor, and graphene oxide (GO)‐stabilized poly(methyl methacrylate) (PMMA) nanoparticles as sacrificial template. The GO‐stabilized PMMA nanoparticles are first prepared and then decorated by a thin PIL coating before carbonization. The resulting NPCs reach a satisfactory specific surface area of up to 561 m2 g−1 and a hierarchically meso‐ and macroporous structure while keeping a nitrogen content of 2.6 wt%. Such NPCs deliver a high reversible charge/discharge capacity of 1013 mA h g−1 over 200 cycles at 0.4 A g−1 for lithium‐ion batteries, and show a good capacity of 204 mA h g−1 over 100 cycles at 0.1 A g−1 for sodium‐ion batteries.

Hierarchical porous N-doped carbon (NPC) is prepared by pyrolysis of poly(- methyl methacrylate) (PMMA) particles decorated by graphene oxide (GO) and polypyrrole (PPy) as precursors and used as anode for lithium-ion batteries. The composite precursors with different diameter and composition (PMMA/GO/ PPy-A and B) were conveniently prepared by dispersion polymerization of methyl methacrylate in the presence of graphene oxide as stabilizer in aqueous medium, followed by addition of pyrrole and its oxidative polymerization. After pyrolysis, the resulting NPC composites with hierarchically structured macro- and mesopores exhibit high surface area (289–398 m2/g) and different N-doping levels (7.46 and 4.22 wt% of nitrogen content). The NPC with the highest N-doping level (7.46 wt%) shows high reversible capacities of 831 mAh/g at 74.4 mA/g (C/5) after 50 cycles and excellent rate performances.

Hydrogels based on polyurethane (PU) are promising (bio-) materials because of their bio- compatibility, biodegradation and excellent mechanical properties. In this publication, polyurethane hydrogels were produced for the first time by a non-isocyanate route by solvent-free step-growth copolymerization between a CO2-sourced hydrophilic polyethy- lene glycol bi-cyclic carbonate with diamines in the presence of a cross-linker. Kinetic of poly(hydroxyurethane) (PHU) synthesis was monitored by ATR-IR and the chemical cross-linking was confirmed by rheology and gel contents measurements. Hydrogels were obtained by immersion of PHUs in water and the influence of the diamine/cross-linker ratio and the nature of diamine on the water swelling and compression properties (compression modulus, strain and stress at break) of PHU hydrogels was evaluated. Additionally, the compression properties of the hydrogels were improved by the addition of Montmorillonite as nanofiller in the PHU formulation. This work opens new application fields for CO2-sourced PHUs.

Original core/corona nanoparticles composed of amaghemite core and a stimuli-responsive polymer coating made of poly(acrylic acid)-block-poly(vinyl alcohol) macromolecules were fabricated for drug delivery system (DDS) application. This kind of DDS aims to combine the advantage of stimuli-responsive polymer coating, in order to regulate the drug release behaviours under different conditions and furthermore, improve the biocompatibility and in vivo circulation half-time of the maghemite nanoparticles. Drug loading capacity was evaluated with methylene blue (MB), a cationic model drug. The triggered release of MB was studied under various stimuli such as pH, ionic strength and temperature. Local heating generated under alternating magnetic field (AMF) application was studied, and remotely AMF-triggered release was also confirmed, while a mild heating-up of the release medium was observed. Furthermore, their potential application as magnetic resonance imaging (MRI) contrast agents was explored via relaxivity measurements and acquisition of T2-weighted images. Preliminary studies on the cytotoxicity against mouse fibroblast-like L929 cell line and also their cellular uptake within human melanoma MEL-5 cell line were carried out. In conclusion, this kind of stimuli-responsive nanoparticles appears to be promising carriers for delivering drugs to some tumour sites or into cellular compartments with an acidic environment.

Reversibly crosslinked poly(vinyl alcohol)-b-poly(N-vinylcaprolactam) PVOH-b-PNVCL nanogels were prepared by using a redox-responsive crosslinking agent, 3,30-dithiodipropionic acid (DPA), to crosslink the PVOH corona, above the lower critical solution temperature (LCST) of the PNVCL block. The stability of the as-prepared nanogels against heating and diluting with water was studied by dynamic light scattering (DLS) to follow the evolution of the hydrodynamic diameter and size distribution. Stability under reductive conditions was also studied by DLS and transmission electron microscopy (TEM) after exposure to dithiothreitol (DTT) buffer solutions at different pH. The reversibility of the crosslinking was evaluated by treating the de-crosslinked nanogels with hydrogen peroxide (H2O2) above the LCST. As a hydrophobic drug model, Nile red (NR) was loaded into the nanogels, and triggered release behaviours were studied after exposure to the same DTT buffer solutions. Moreover, two PVOH-b-PNVCL copolymers with different compositions and LCST were used to evaluate the effect of the LCST on the release behaviours of the nanogels. The cytotoxicity of the nanogels against a mouse fibroblast-like L929 cell line was assessed via the MTS assay, and preliminary studies on cellular uptake of the nanogels within human melanoma MEL-5 cells were also carried out by fluorescence microscopy and fluorescence-activated cell sorting.

Organometallic-mediated radical polymerization (OMRP) has seen a significant growth in the last years notably due to the development of new metal complexes, especially cobalt derivatives. Despite of this, none of the reported complexes offers optimal control for monomers with very different reactivity, which somewhat limits the synthesis of copolymers. In order to expand the scope of cobalt-mediated radical polymerization (CMRP), we investigated an in situ ligand exchange reaction for modulating the properties of the cobalt complex at the polymer chain-end and adjusting the C-Co bond strength involved in the control process. With the aim of improving the synthesis of poly(vinyl acetate)-b-poly(n-butyl acrylate) copolymers, bidentate acetylacetonate ligands, which impart high level of control to the polymerization of vinyl acetate (VAc), were replaced in situ at the PVAc-cobalt chain-end by tetradentate Salen type ligands that are more suited to acrylates.

Reversibly crosslinked (RCL) nanogels made of thermo-responsive poly(vinyl alcohol)-b-poly(Nvinylcaprolactam) copolymers were combined with maghemite nanoparticles and developed as new drug delivery systems (DDS). The crosslinking was formed via boronate/diol bonding from the surfacefunctionalized superparamagnetic maghemite nanoparticles, endowing the DDS with thermo-, pH- and glucose-responsiveness. The capability to load a hydrophobic drug model Nile red (NR) within the RCL nanogels was evaluated, and stimuli-triggered drug release behaviours under different conditions were tested. Zero premature release behaviour was detected at physiological pH in the absence of glucose, whereas triggered release was observed upon exposure to acidic pH (5.0) and/or in the presence of glucose. In light of the superparamagnetic properties of the maghemite nanoparticles and RCL nanogels, magnetically-induced heating, MR imaging performance, as well as remotely magnetically-triggered drug release under alternating magnetic field (AMF), were investigated. Cytotoxicity against fibroblast-like L929 and human melanoma MEL-5 cell lines was assessed via the MTS assay. In vitro stimuli-triggered release of tamoxifen, a chemotherapeutic drug, was also studied within MEL-5 cell cultures under different conditions. These innovative RCL nanogels, integrating different stimuli-responsive components, hydrophobic chemotherapeutic moieties and also diagnostic agents together via reversible crosslinking, are promising new theranostic platforms.

Poly(N-vinylcaprolactam) (PNVCL) and poly(N-vinylpyrrolidone) (PNVP) are water soluble polymers of interest especially in the biomedical field. Moreover, PNVCL is characterized by a lower critical solution temperature close to 36 °C in water, which makes it useful for the design of thermoresponsive systems. In this context, we used the cobalt-mediated radical polymerization (CMRP) and reaction coupling (CMRC) for synthesizing a series of well-defined NVCL and NVP-based copolymers, including statistical copolymers as well as double thermoresponsive diblocks and triblocks. Dynamic light scattering and turbidimetry analyses highlighted the crucial impact of the copolymer composition and architecture on the cloud point temperature (TCP) of each segment and also their influence on the multistep assembly behaviour of block copolymers. Addition of NaCl enabled us to adjust the inter-TCP range of the di- and triblock in which selective precipitation of one block and self-assembly of the copolymer were favoured. Overall, data presented here provide a basis for the synthesis of a broad range of NVCL/NVP based copolymer architectures with a tunable thermal response in water.

The photoinitiated cobalt-mediated radical polymerization enables the synthesis of novel alpha-functional and alpha,omega-telechelic polymers. In combination with ring-opening polymerization, it also produces new amphiphilic copolymers which self-assemble into flower-like vesicles in water.

The organometallic-mediated radical polymerization (OMRP) of N-vinyl-3-alkylimidazolium-type monomers, featuring the bis(trifluoromethylsulfonyl)imide counteranion (Tf2N–), in the presence of Co(acac)2 as controlling agent, is reported. Polymerizations of monomers with methyl, ethyl, and butyl substituents are fast, reaching high monomer conversion in ethyl acetate as solvent at 30 °C, and afford structurally well-defined hydrophobic poly(ionic liquid)s (PILs) of N-vinyl type. Block copolymer synthesis is also achieved by sequential OMRP of N-vinyl-3-alkylimidazolium salts carrying different alkyl chains and different counteranions (Tf2N– or Br–). These block copolymerizations are carried out at 30 °C, either under homogeneous solution in methanol or in a biphasic medium consisting of a mixture of ethyl acetate and water. Unprecedented PIL-b-PIL block copolymers are thus prepared under these conditions. However, anion exchange occurs at the early stage of the growth of the second block. Finally, diblock copolymers generated in the biphasic medium can be readily coupled by addition of isoprene, forming all PIL-based and symmetrical ABA-type triblock copolymers in a one-pot process. Such a direct block copolymerization method, involving vinylimidazolium monomers bearing different alkyl chains, thus opens new opportunities in the precision synthesis of all PIL-based block copolymers of tunable properties.

The isoprene-assisted radical coupling (I-ARC) of polymers prepared by cobalt-mediated radical polymerization (see picture) is the first efficient radical coupling method that is not restricted to short chains. When applied to AB diblock copolymers, I-ARC constitutes a straightforward approach to the preparation of novel symmetrical ABA triblock copolymers

iving/controlled polymerization methods have enabled the synthesis of numerous (co)polymers with defined compositions and architectures. However, the precision design of poly(vinylamine)-based copolymers remains challenging despite their extensive use in various fields of applications and the clear benefits to finely tune their properties. Here, we report on a two-step strategy for the synthesis of tailor-made poly(vinylamine) derivatives through the organometallic- mediated radical (co)polymerization (OMRP) of N-vinyl- acetamide and/or N-methylvinylacetamide followed by acid hydrolysis of the acetamide groups. A series of well-defined homopolymers as well as statistical and block copolymers with pendant primary and/or secondary amines having controlled molar masses, compositions, and low dispersities were produced accordingly. The reactivity ratios of the comonomers as well as the composition drift along the chain were determined in order to have a precise idea of the polymer structures. These advances represent a significant step toward an efficient platform for synthesis of this important class of amino group-containing (co)polymers.

Amphiphilic double poly(ionic liquid) (PIL) block copolymers are directly prepared by cobalt- mediated radical polymerization induced self-assembly (CMR-PISA) in water of N-vinyl imida- zolium monomers carrying distinct alkyl chains. The cobalt-mediated radical polymerization of N-vinyl-3-ethyl imidazolium bromide (VEtImBr) is first carried out until high conversion in water at 30 °C, using an alkyl bis(acetylacetonate)cobalt(III) adduct as initiator and con- trolling agent. The as-obtained hydrophilic poly(N-vinyl-3- ethyl imidazolium bromide) (PVEtImBr) is then used as a macroinitiator for the CMR-PISA of N-vinyl-3-octyl imidazo- lium bromide (VOcImBr). Self-assembly of the amphiphilic PVEtImBr-b-PVOcImBr block copolymer, i.e., of PIL-b-PIL-type, rapidly takes place in water, forming polymer nanoparticles consisting of a hydrophilic PVEtImBr corona and a hydro- phobic PVOcImBr core. Preliminary investigation into the effect of the size of the hydrophobic block on the dimension of the nanoparticles is also described.

Thermo-responsive block copolymers based on poly(N-vinylcaprolactam) (PNVCL) have been prepared by cobalt-mediated radical polymerization (CMRP) for the first time. The homopolymerization of NVCL was controlled by bis(acetylacetonato)cobalt(II) and a molecular weight as high as 46,000 g/mol could be reached with a low polydispersity. The polymerization of NVCL was also initiated from a poly(vinyl acetate)-Co(acac)2 (PVAc-Co(acac)2) macroinitiator to yield well-defined PVAc-b-PNVCL block copolymers with a low polydispersity (Mw/Mn = 1.1) up to high molecular weights (Mn = 87,000 g/mol), which constitutes a significant improvement over other techniques. The amphiphilic PVAc-b-PNVCL copolymers were hydrolyzed into unprecedented double hydrophilic poly(vinyl alcohol)-b-PNVCL (PVOH-b-PNVCL) copolymers and their temperature-dependent solution behavior was studied by turbidimetry and dynamic light scattering. Finally, the so-called cobalt-mediated radical coupling (CMRC) reaction was implemented to PVAc-b-PNVCL-Co(acac)2 precursors to yield novel PVAc-b-PNVCL-b-PVAc symmetrical triblock copolymers.

Transition metal-assisted polymerization techniques have always played a crucial role in polymer synthesis. As an illustration, metallic compounds have deeply marked the field of living/controlled radical polymerization (L/CRP) which gives access to well-defined polymers under non drastic conditions. Indeed, atom transfer radical polymerization (ATRP) is one of the most successful methods to polymerize vinyl monomers in a controlled manner. Besides this very successful system, another metal-assisted CRP technique is emerging, i.e. organometallic-mediated radical polymerization (OMRP). In contrast to ATRP, OMRP involves the reversible formation of a covalent bond between a transition metal and the polymer chains, which strongly decreases the extent of termination reactions and leads to polymers with predictable molecular weights. This lecture aims to provide a comprehensive overview of the synthetic and mechanistic aspects of OMRP as well as major achievements and remaining challenges in this field.

This review focuses on an emerging class of controlled radical polymerization named Organometallic-Mediated Radical Polymerization (OMRP). The latter is based on the temporary deactivation of the growing radical species by a transition metal complex and the reversible formation of a carbon-metal covalent bond. Initially developed with cobalt complexes, OMRP has extended to several metals today. As highlighted here, the choice of the metal, the structure of ligands, temperature, and additives deeply affect the course of the polymerization and its mechanism. Macromolecular engineering opportunities offered by OMRP are also described, as well as practical applications sustained by the resulting polymer materials.

The cobalt mediated radical polymerization (CMRP) of vinyl chloride (VC) in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) as a controlling agent is presented for the first time. Using an alkyl-Co(III) compound (R0–(CH2–CHOAc)<4–Co(acac)2; R0 = (H3C)2(OCH3)C–CH2–C(CH3)(CN)–) as an initiator, the bulk polymerization under non-isotherm conditions is controlled. 1H NMR spectra of the resulting PVC show that the CMRP process does not significantly affect the level of defects compared to a PVC prepared by a conventional free radical polymerization at the same temperature. Using the same alkyl-cobalt(III) compound, the copolymerization of VC and VAc is controlled at 40 °C provided that enough VAc (about 40 mol%) is present in the polymerization medium to moderate the VC polymerization. In line with reactivity ratios, VC is preferentially incorporated in the polymer at the early stages of the polymerization, leading to copolymers with a high VC content at moderate conversions. This is the first report of a CMRP of VC and of the synthesis of well-defined statistical PVC-co-PVAc copolymers by this technique.

Cobalt-mediated radical coupling (CMRC) is successfully applied to poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone) (PNVP) precursors for the first time. The coupling process is based on addition of isoprene onto polymer chains preformed by controlled radical polymerization with cobalt complexes (CMRP). The extents of coupling were high (>90%) to moderate (75-80%) for PVAc and PNVP precursors, respectively. Effects of the length of the polymer precursors and conditions used in the polymerization step on the coupling efficiency are discussed. Mass spectrometry (MS) and nuclear magnetic resonance (NMR) analyses conducted on the coupling products demonstrate the preferential insertion of two isoprene units in the final polymers. The CMRC mechanistic proposal, supported by DFT calculations, is based on this microstructure feature. Finally, illustration of the macromolecular engineering potential of this technique is given by the preparation of symmetrical PVAc-b-PNVP-b-PVAc triblock copolymers starting from the corresponding PVAc-b-PNVP-[Co] diblock copolymer.

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)2]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 °C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected solvent effect that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP.

In situ combination of a polymerization step with a coupling reaction is demonstrated to accelerate the synthesis protocols for symmetrical multiblock copolymers. Predici simulations and experiments prove on the example of cobalt-mediated radical polymerization and coupling (CMRP/C) reactions that such synthesis strategy can be very effective and easy to conduct. Treatment of a cobalt-terminated poly(acrylonitrile) precursor with a mixture of acrylate and isoprene led to the rapid polymerization of the acrylate before isoprene-assisted radical coupling of the macroradical chains forming a well-defined poly(acrylonitrile)-b-poly(acrylate)-b-poly(acrylonitrile) triblock. The degree of polymerization of the central block, resulting from the balance between propagation and coupling, could be tuned by adjusting the relative concentration and varying the structure of the acrylate and diene. The same convergent strategy also permits the synthesis of ABCBA-type pentablock copolymer starting from a cobalt-functional diblock. Simultaneous radical polymerization and coupling is thus a powerful macromolecular engineering approach for the straightforward design of symmetrical multiblock copolymers.

Novel organocobalt complexes featuring weak C–CoL2 bonds (L = acetylacetonate) are prepared and used as sources of halomethyl radicals. They permit the precision synthesis of a-halide functionalized and telechelic polymers in organic media or in water. Substitution of halide by azide allows derivatization of polymers using the CuAAC click reaction.

Recent developments in cobalt-mediated radical polymerization (CMRP) and progress in the mechanistic understanding enabled to optimize the copolymerization of n-butyl acrylate (nBA) with vinyl acetate (VAc), as well as to control the homopolymerization of nBA by means of bis(acetylacetonato)cobalt-(II) (Co(acac)2). Critical experimental parameters such as the initiating system, the temperature, and the presence of additives were varied and discussed. Under optimized conditions, an alkylcobalt(III) adduct R0-(CH2-CHOAc)<4-Co(acac)2 (R0=primary radical from the V-70 decomposition) allowed a better control of the nBA/VAc copolymerization than the previously studied V-70/Co(acac)2 pair regarding the molecular weight control and the polydispersities. Importantly, the homopolymerization of nBA was controlled by Co(acac)2 for the first time using the alkylcobalt(III) adduct or the lauroyl peroxide (LPO)/ Co(acac)2 redox pair as initiating system. Typically, poly(n-butyl acrylate) with polydispersity around 1.2 and molar mass as high as 200 000 g/mol was achieved with this cobalt complex.

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by reduction by sodium borohydride. After deposition of the so-loaded micelles onto a silicon wafer, followed by an appropriate thermal treatment, the poly(acrylonitrile) core of the micelles is carbonized, while the poly(vinyl alcohol) shell is completely decomposed and volatilized, leading to gold encapsulated in carbon nanoparticles. The morphology of the micelles is maintained during thermal treatment without requiring shell-cross-linking of the micelles prior to pyrolysis.

Mesoporous carbon fibers were prepared by controlled pyrolysis of poly(vinyl acetate)-b-poly(acrylonitrile) (PVAc-b-PAN) copolymer located inside a cylindrical nanoporous template. A melt-compression method was developed to help the penetration of the infusible copolymer inside the template without the use of any solvent that ensures the formation of completely filled fibers instead of nanotubes. The influence of the composition of the PVAc-b-PAN copolymer and the heating rate during pyrolysis on the porous morphology of the fibers was studied by transmission electron microscopy (TEM).

Graft copolymers have been prepared by one-step organometallic-mediated radical polymerization (OMRP) for the first time. Poly(ethylene glycol) acrylate (PEGA) was copolymerized with vinyl acetate (VAc) to yield well-defined P(PEGA-grad-VAc) gradient graft copolymers using bis(acetylacetonato)cobalt(II) as the control agent. The influence of experimental parameters such as the PEGA/VAc molar ratio, the nature of the initiator, and the temperature on the control of the copolymerization was discussed. The use of an excess of cobalt complex appeared as a key parameter to maintain a good level of control when higher contents of acrylate were used in the comonomer feed. The reactivity ratios were estimated and revealed that PEGA was added around 30 times faster than VAc, which gave access to a gradient P(PEGA-grad-VAc) copolymer or to a P(PEGA-grad-VAc)-b-PVAc diblock copolymer when the VAc polymerization was pursued after the full consumption of PEGA. The amphiphilic character of the copolymers makes them prone to self-assemble into micelles in water, as evidenced by dynamic light scattering.

Via consecutive cobalt-mediated radical polymerization (CMRP), nitrone-mediated radical coupling (NMRC) and copper catalyzed azide-alkyne cycloaddition (CuAAC), polymers with mikto-arm star and H-shape architecture were synthesized. Poly(vinyl acetate)40-block-poly(acrylonitrile)78-Co(acac)2 polymers were synthesized via CMRC and subsequently coupled using an alkyne functional nitrone. The coupling efficiency of the NMRC process was assessed employing N-tert-butyl a-phenyl nitrone (PBN), which is structurally very similar to the later employed coupling agent. Generally, coupling efficiencies of close to 90% or higher were observed in all cases. Since the coupling reaction yields triblock copolymers bearing an alkoxyamine functionality (and thus also an alkyne group) in the middle of the chain, well defined PEG conjugates could be obtained via CuAAC. Miktoarm star polymers of the structure (PVAc-b-PAN)2-PEG were generated as well as H-shaped material of the structure (PVAc-b-PAN)2-PEG-(PVAc-b-PAN)2 via conjugation with bifunctional PEG. In all cases, very narrow molecular weight material was obtained. Molecular weight analysis of the intermediate and the final products reveals that the hydrodynamic volume of the miktoarm star and the H-shaped materials is not substantially increased during the final conjugation reaction despite the fact that the absolute molecular weight increases by more than a factor of two in the latter case. Success of the conjugation reactions was confirmed via composition analysis via NMR.

The implementation of cobalt-mediated radical polymerization (CMRP) for continuous microreactor synthesis is described. We demonstrate how the utilization of flow photoreactors allows the speed up of the polymerization of vinyl acetate (VAc) under UV irradiation without loss of polymerization control. Microfluidics under UV irradiation has also been successfully implemented for the copolymerization of VAc with a less reactive olefin 1-octene (1-Oct). Reactivity ratios were deduced for this copolymerization system, and poly(VAc-co-1-Oct) copolymers containing up to 50 mol% of 1-Oct were synthesized. To the best of our knowledge, this is the first report on a photopolymerization where continuous flow techniques not only led to an improvement of reaction rates and dispersity, but also led to the avoidance of significant side-products that were observed in batch processing

The synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) (PVAc-b-PVC) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP) is investigated for the first time in this paper. A PVAc–Co(acac)2 macroinitiator is prepared by CMRP using the V-70/Co(acac)2 binary system or a preformed alkylcobalt(III) compound. Then, the block copolymerization occurs in the bulk at 40 °C by the addition of VC. The addition of water to the polymerization medium or the slow generation of alkyl radicals during the whole polymerization is beneficial to the process by consuming part of the excess of deactivator (Co(acac)2) that blocks the polymer chains into the dormant form. Dynamic light scattering (DLS) measurements and AFM analyses evidence that the PVAc-b-PVC forms core–shell micelles in a selective solvent of the PVAc block, i.e. methanol, evidencing the blocky structure of the copolymer. PVAc-b-P(VC-co-VAc) copolymers are also successfully prepared by initiating the radical copolymerization of VC and VAc at 40 °C from a PVAc–Co(acac)2 macroinitiator.

Poly( N -vinylcaprolactam) (PNVCL) is a thermoresponsive and biocompatible polymer that raises an increasing interest in the biomedical area, especially in drug delivery systems (DDS) that include micelles, hydrogels, and hybrid particles. The thermoresponsiveness of PNVCL, used alone or in combination with other stimuli- responsive polymers or particles (pH, magnetic fi eld, or chemicals), is often key in the loading and/or release process in these DDS. The renewed focus on this polymer, which is known for decades, is to a large extent due to recent progress in synthetic strategies. Especially, the advent of efficient controlled radical polymerization (CRP) methods for NVCL monomer gives now access to unprecedented well-defi ned NVCL-based copolymers with unique properties. This Review article addresses up-to-date synthetic aspects, biological features, and biomedical applications of the latest NVCL-containing systems.

Combining the redox activity and remarkable adhesion propensity of polyphenols (such as catechol or pyrogallol) with the numerous tunable properties of poly(ionic liquid)s (PILs) is an attractive route to design inventive multifunctional macro-molecular platforms. In this contribution, we describe the first synthesis of a novel family of structurally well-defined PILs functionalized with catechol/pyrogallol/phenol pendants by organometallic-mediated radical polymerization (OMRP) using an alkyl−cobalt(III) complex as initiator and mediating agent. The living character of the chains is also exploited to produce di-and triblock PILs, and the facile counteranion exchange reactions afforded a library of PILs-bearing free phenol/catechol/pyrogallol moieties. Electrochemical investigations of catechol/pyrogallol-derived PILs in aqueous medium demonstrated the characteristic catechol to o-quinone transformations, whereas, quasi-reversible doping/undoping with supporting electrolyte cations (Li + /tetrabutylammonium +) has been observed in organic media, suggesting a bright future for this new family of redox-active PILs as cathode material for secondary energy storage devices. Also, pendant catechol/pyrogallol groups mediated sustained anchoring onto the gold surface conferred PILs properties to the interface. As a proof-of-concept, both the adsorption and inhibition of proteins on polymer modified surfaces have been demonstrated in real time using the quartz crystal microbalance with dissipation technique. The exquisite physicochemical tunability of these innovative surface-and redox-active PILs makes them excellent candidates for a broad range of potential applications, including " smart surfaces " and electrochemical energy storage devices.

The controlled polymerization of vinyl acetate has been recently achieved by several techniques, but PVAc with targeted Mn and low dispersity up to very high monomer conversions and high degrees of polymerization was only obtained with Co(acac)2 as controlling agent in the so-called CMRP, a type of organometallic mediated radical polymerization (OMRP). Other techniques (including ATRP, ITP, TERP, and RAFT/MADIX) have shown a more or less pronounced slowdown in the polymerization kinetics, which was attributed to the higher strength of the C−X bond between the radical PVAc chain and the trapping agent (X) in the dormant species and to a consequent slower reactivation after a less frequent head-to-head monomer addition. The reason for the CMRP exception is clarified by the present contribution. First, a detailed investigation by 1H, 13C and multiplicity-edited HSQC and DEPT-135 NMR of the PVAc obtained by CMRP, in comparison with a regular polymer made by free radical polymerization under the same conditions, has revealed that Co(acac)2 does not significantly alter the fraction of head-to-head sequences in the polymer backbone and that there is no accumulation of Co(acac)2-capped chains with a head-to-head ω end. Hence, both dormant chains (following the head-to-head and the head-to-tail monomer additions) must be reactivated at similar rates. A DFT study shows that this is possible because the dormant chains are stabilized not only by the C−Co σ bond but also by formation of a chelate ring through coordination of the ω monomer carbonyl group. The head-to-head dormant chain contains an inherently stronger C−Co bond but forms a weaker 6-membered chelate ring, whereas the weaker C−Co bond in the head-to-tail dormant chain is compensated by a stronger 5-membered chelate ring. Combination of the two effects leads to similar activation enthalpies, as verified by DFT calculations using a variety of local, gradient-corrected, hybrid and “ad hoc” functionals (BPW91, B3PW91, BPW91*, M06 and M06L). While the BDE(C−X) of model H-VAc−X molecules [X = Cl, I, MeTe, EtOC(S)S and Co(acac)2] are functional dependent, the BDE difference between head-to-head and head-to-tail dormant chain models is almost functional insensitive, with values of 5−9 kcal/mol for the ATRP, ITP and TERP models, 3−6 for the RAFT/MADIX model, and around zero for CMRP.

The precision synthesis of poly(ionic liquid)s (PILs) in water is achieved for the first time by the cobalt-mediated radical polymerization (CMRP) of N-vinyl-3-alkylimidazolium-type monomers following two distinct protocols. The first involves the CMRP of various 1-vinyl-3-alkylimidazolium bromides conducted in water in the presence of an alkyl–cobalt(III) complex acting as a monocomponent initiator and mediating agent. Excellent control over molar mass and dispersity is achieved at 30 °C. Polymerizations are complete in a few hours, and PIL chain-end fidelity is demonstrated up to high monomer conversions. The second route uses the commercially available bis(acetylacetonato)cobalt(II) (Co(acac)2) in conjunction with a simple hydroperoxide initiator (tert-butyl hydroperoxide) at 30, 40, and 50 °C in water, facilitating the scaling-up of the technology. Both routes prove robust and straightforward, opening new perspectives onto the tailored synthesis of PILs under mild experimental conditions in water.

Cobalt-mediated radical polymerization (CMRP) and tellurium-mediated radical polymerization (TERP) were combined for the first time, offering new perspectives in the precision design of macromolecular structures. In particular, the present work highlights the benefits of this strategy for the synthesis of novel poly(vinyl acetate)-based block copolymers. A range of well-defined poly(vinyl acetate)s (PVAc) were first produced via CMRP using the bis(acetylacetonato)cobalt(II) complex (Co(acac)2) as a regulating agent. Substitution of a methyltellanyl moiety for Co(acac)2 at the ω-chain end of the precursor was then achieved upon treatment with dimethylditelluride. In contrast to the PVAc prepared by TERP, the ones produced by sequential CMRP and Co/Te exchange reaction almost exclusively consist of regular head-to-tail-TeMe chain-end species that can be activated by TERP. Ultimately, a series of monomers problematic in Co(acac)2-mediated radical polymerization including N-isopropylacrylamide (NIPAM), 2-(dimethylamino)ethyl acrylate (ADAME), n-butyl acrylate (BA), isoprene (IP), and vinylimidazole (NVIm) were polymerized by TERP from the PVAc–TeMe macroinitiators leading to novel diblock copolymers that cannot be made by each technique used separately.

Controlled radical polymerization (CRP) techniques offer the opportunity to properly design polymer chains and adjust their chemical and physical properties. Among these techniques, cobalt-mediated radical polymerization (CMRP) distinguished itself by the high level of control imparted to the polymerization of acrylic and vinyl ester monomers, even for high molar masses. This article summarizes for the first time the advances in understanding and synthetic scope of CMRP since its discovery. Notably, the cobalt–carbon bond formation by dual contribution of reversible termination and degenerative chain transfer is discussed, as well as the impact of additives able to coordinate the metal. The potential of computational chemistry in the field of CMRP as a rationalization and predicting tool is also presented. These mechanistic considerations and achievements in macromolecular engineering will be discussed along with challenges and future prospects in order to assess the CMRP system as a whole.

The input of photochemistry to the Co(acac)2 mediated radical polymerization (CMRP) of n-butyl acrylate and vinyl acetate is investigated for the first time. Upon UV irradiation, photoinitiators are able to initiate the n-butyl acrylate polymerization that remains controlled up to very high molar masses (>4 × 106 g mol−1) with low polydispersities. The photoinitiator as well as the irradiation time must be appropriately chosen to reach acceptable initiator efficiencies while maintaining an optimal control over the polymerization. Laser flash photolysis experiments were then carried out to evidence the addition of alkyl and phosphonyl radicals onto Co(acac)2 and to determine the rate constants (kdeact) of these addition reactions that were still lacking. Finally, both kinetics of polymerization and spin-trapping experiments have evidenced that the C–Co bond at the extremity of the dormant polymer chains can be easily photocleaved. UV irradiation can therefore be considered as an additional lever for tuning the reactivity of the CMRP process mediated by Co(acac)2.

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.

Cobalt-mediated radical coupling (CMRC) is a straightforward approach to the synthesis of symmetrical macromolecules that relies on the addition of 1,3-diene compounds onto polymer precursors preformed by cobalt-mediated radical polymerization (CMRP). Mechanistic features that make this process so efficient for radical polymer coupling are reported here. The mechanism was established on the basis of NMR spectroscopy and MALDI-MS analyses of the coupling product and corroborated by DFT calculations. A key feature of CMRC is the preferential insertion of two diene units in the middle of the chain of the coupling product mainly according to a trans-1,4-addition pathway. The large tolerance of CMRC towards the diene structure is demonstrated and the impact of this new coupling method on macromolecular engineering is discussed, especially for midchain functionalization of polymers. It is worth noting that the interest in CMRC goes beyond the field of polymer chemistry, since it constitutes a novel carbon-carbon bond formation method that could be applied to small organic molecules.

In this communication, we prepared carbon nanotubes (CNTs) modified by poly(vinyl alcohol) that are used as co-stabilizers for the dispersion polymerization of methyl methacrylate. Poly(methyl methacrylate) microspheres with CNTs selectively located at their surface are formed. This specific localization is a way to enhance the electrical conductivity of the nanocomposite.

The grafting mechanism of poly(vinyl acetate) macroradicals prepared by cobalt-mediated radical polymerization onto C60 is investigated. The experimental conditions directly impact the nature and stability of the PVAc/C60 adducts. In the presence of residual initiating radicals that can compete with PVAc! macroradicals for addition onto C60, mixtures of PVAc/C60 adducts having between one and eight polymer chains per C60 are formed. PVAc/C60 adducts prepared with low [PVAc]:[C60] ratios may contain weak C60-C60 bonds that further dissociate and account for the instability of the products. The formation of such dimers can be lessened by increasing the temperature from 30 !C to 100 !C. The temperature increase also allows a complete dissociation of the PVAc-Co dormant species into PVAc! macroradicals and an almost quantitative grafting of eight PVAc chains onto C60, leading to well-de!ned C60(PVAc)8 octa-adducts. These results might shed new light on the grafting onto C60 of macroradicals prepared by other CRP techniques.

N-Vinylcaprolactam (NVCL) was copolymerized statistically for the first time in a controlled manner with hydrophilic N-vinylamide or hydrophobic vinylester monomers in order to precisely tune up and down the lower critical solution temperature (LCST) of the resulting copolymers. The incorporation of these segments in complex architectures was also considered. Several narrowly distributed NVCL-based copolymers were prepared by cobalt-mediated radical polymerization (CMRP) using the bis-(acetylacetonato)cobalt(II) complex as a controlling agent and N-methyl-N-vinylacetamide (NMVA), N-vinylacetamide (NVA), vinyl acetate (VAc) or vinyl pivalate (VPi) as comonomers. PNVCL-containing block copolymers having two discrete LCSTs were also synthesized following a one-pot strategy based on the sequential CMRP of NVCL followed by the copolymerization of NMVA with the residual NVCL. Upon gradual heating of aqueous solutions of such double thermoresponsive copolymers, we noticed a transition from free chains to micelles before full dehydration and collapse of the block copolymers. These advances represent a significant step towards the development of a platform based on thermoresponsive PNVCL copolymers with a single phase separation or multistep assembly behaviors.

The cobalt-mediated radical polymerization (CMRP) of 1-vinyl-3-ethylimidazolium bromide (VEtImBr) is described. Polymerizations were performed at 30 °C in solution either in dimethylformamide (DMF) or in methanol (MeOH) or in a mixture of both solvents, using a preformed alkyl–cobalt(III) adduct, CH3OC(CH3)2CH2–C(CH3)(CN)–(CH2–CHOAc)<4–Co(acac)2, as the mediating agent. Excellent control over molecular weights and dispersities (Mw/Mn 1.05–1.06) was achieved in MeOH, with a linear increase of experimental molecular weights with the monomer conversion. Substituting methanol for DMF induced much faster polymerization process, even under quite high diluted conditions: for instance, about 80% monomer conversion was reached in 30 min in DMF, compared to 10 h in MeOH. However, size exclusion chromatography (SEC) traces of PVEtImBr samples synthesized in DMF revealed a side population in the high molecular weight region, presumably due to the occurrence of irreversible coupling reactions of a small proportion of growing chains. Well-defined diblock copolymers featuring both a poly(vinyl acetate) (PVAc) block and a PVEtImBr-based poly(ionic liquid) block, PVAc-b-PVEtImBr, were next obtained by sequential CMRP of VAc and VEtImBr. To this end, a PVAc-Co(acac)2 was first prepared by CMRP and employed as a macroinitiator for the polymerization of VEtImBr either in methanol or in a mixture of DMF and MeOH (2/1: v/v) at 30 °C. Finally, cobalt-mediated radical coupling (CMRC) of the aforementioned PVAc-b-PVEtImBr diblock copolymers, using isoprene as a simple coupling agent, led to unprecedented and structurally well-defined PVAc-b-PVEtImBr-b-PVAc triblock copolymers.

This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex, i.e. the bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered in order to evidence the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidone < N-vinyl caprolactam < N-methyl-N-vinyl acetamide, and is responsible for the optimal control of the polymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, via a covalent bond and a dative one, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. The possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding factors influencing a Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide)s, an important class of polymers which sustains numerous applications today.

Access to well-defined polymers made of the so-called ‘Less Activated Monomers’ (LAMs) via controlled radical polymerization has long been a challenge due to the lack of radical stabilizing group on the double bond of these monomers. This Feature Article summarizes substantial progress in the organometallic-mediated radical polymerization (OMRP) of this important class of monomers including vinyl esters, olefins, vinyl chloride, vinyl amides, or ionic-liquid vinyl monomers. It aims to provide a clear and comprehensive account of the fundamentals and challenges in the OMRP of LAMs as well as an overview of the resulting macromolecular engineering opportunities. The input of photochemistry, environmentally friendly solvents or flow reactors in OMRP is also presented. Finally, it emphasizes how some well-defined LAMs-based materials contributed to the development of specific applications notably in the fields of biomedicine or energy.

The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

Core–corona gold/poly(vinyl alcohol)-b-poly(N-vinylcaprolactam) nanoparticles (gold@PVOH-b-PNVCL NPs) were fabricated via an in situ method, where a gold salt was reduced within the macromolecular aqueous solution. Arrangement of macromolecular chains on the surface of gold cores was studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy and infrared spectroscopy. The responsiveness to temperature and the preserved colloidal stability of the gold@PVOH-b-PNVCL NPs above the lower critical solution temperature (LCST) were confirmed by dynamic light scattering and turbidity measurements. The drug loading capacity (DLC of ca. 1.3–2.8 wt%) of the gold@PVOH-b-PNVCL NPs as a drug delivery system (DDS) was tested with Nadolol®, a hydrophilic drug, and the release behaviours were studied at several temperatures. PVOH-b-PNVCL copolymers with an LCST of a few degrees above the biological temperature (37 °C), for example, PVOH180-b-PNVCL110 (LCST of 41 °C), are preferential, due to the slower release at 37 °C, but a faster release at temperatures that are a few degrees higher. The cytocompatibility of the gold@PVOH-b-PNVCL NPs against mouse fibroblastic L929 cells was evaluated via the MTS assay. Cellular uptake within MEL-5 human melanoma cells was studied by confocal laser scanning microscopy, fluorescence-activated cell sorting and TEM techniques and it showed that gold@PVOH-b-PNVCL NPs preferably accumulated within the cellular cytoplasm, with an incubation concentration and period-dependent uptake process. All these results corroborated a general utility of these thermo-responsive gold@PVOH-b-PNVCL NPs for drug delivery and controlled drug release.

Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO 2 ). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2 . Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass ( Mn ) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for M n up to 10 000 g mol−1 , but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2 , is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents.

New micellar macrocontrast agents with improved contrast at high frequencies were designed by grafting a gadolinium based contrast agent onto functional stealth micelles formed by poly(ethylene oxide)-b-poly(ε-caprolactone) (PEO-b-PCL) in water. As evidenced by relaxometry measurements and the hemolytic CH50 test, the new contrast agents are of interest as MRI blood pool agents.

Stealth macromolecular platforms bearing alkyne groups and poly(ethylene oxide) brushes were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. The anchoring of Gd3+-chelates bearing an azide group was then carried out by the Huisgen 1,3-dipolar cycloaddition (“click”) reaction in mild conditions, leading to macrocontrast agents for MRI applications. The gadolinium complex is hidden in the PEO shell that renders the macrocontrast agents free of any cytotoxicity and stealth to proteins of the immune system. Relaxometry measurements have evidenced an improved relaxivity of the macrocontrast agent compared to ungrafted gadolinium chelate. Moreover, this relaxivity is further enhanced when the spacer length between the Gd3+-chelate and the polymer backbone is shorter, as the result of its decreased tumbling rate. These novel products are therefore promising candidates for MRI applications.

New hydrosoluble magnetic resonance imaging (MRI) macrocontrast agents are synthesized by reversible addition fragmentation chain transfer (RAFT) copolymerization of poly(ethylene oxide) methyl ether acrylate (PEOMA) with an acrylamide bearing a ligand for gadolinium, followed by the complexation of Gd3+. This convenient and simple grafting through approach leads to macrocontrast agents with a high relaxivity at high frequency that is imparted by the restricted tumbling of the Gd3+ complex caused by its attachment to the polymer backbone. Importantly a very low protein adsorption is also evidenced by the hemolytic CH50 test. It is the result of the poly(ethylene oxide) (PEO) brush that efficiently hides the gadolinium complex and renders it stealth to the proteins of the immune system. Improved contrast and long blood circulating properties are thus expected for these macrocontrast agents.

Conventional low molecular weight gadolinium based Magnetic Resonance Imaging (MRI) contrast agents such as Magnevist® are very useful for imaging tissues. However, at the high magnetic fields used in modern MRI equipments, their relaxivity (contrasting efficiency) is rather poor. The grafting of the gadolinium complex onto macromolecules is a way to enhance their relaxivity provided that the rotational motion of the complex is decreased significantly. Here we report the design of novel Gd3+ based MRI contrast agents with improved relaxivity and potential long blood circulation life-time. We investigate the grafting of 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid, 1,4,7-tris(1,1-dimethylethyl) ester (DO3AtBu-NH2; a precursor of Gd3+ ligand) onto well-defined functional copolymers bearing activated esters (succinimidyl esters) and poly(ethylene oxide) (PEO) chains required for stealthiness. The tert-butyl groups of grafted DO3AtBu-NH2 are then deprotected by trifluoroacetic acid followed by complexation of Gd3+. Addition of free DOTA at the end of the reaction is necessary to leave the pure and stable water soluble macrocontrast agent. Importantly it shows a relaxivity at high frequencies that is 300% higher than that of the ungrafted gadolinium complex. These novel functional copolymers are therefore promising candidates as macromolecular contrast agents for MRI applications.

It is well known in industrial applications involving powders and granular materials that the relative air humidity and the presence of electrostatic charges influence drastically the material flowing properties. The relative air humidity induces the formation of capillary bridges and modify the grain surface conductivity. The presence of capillary bridges produces cohesive forces. On the other hand, the apparition of electrostatic charges due to the triboelectric effect at the contacts between the grains and at the contacts between the grains and the container produces electrostatic forces. Therefore, in many cases, the powder cohesiveness is the result of the interplay between capillary and electrostatic forces. Unfortunately, the triboelectric effect is still poorly understood, in particular inside a granular material. Moreover, reproducible electrostatic measurements are difficult to perform. We developed an experimental device to measures the ability of a powder to charge electrostatically during a flow in contact with a selected material. Both electrostatic and flow measurements have been performed in different hygrometric conditions. The correlation between the powder electrostatic properties, the hygrometry and the flowing behavior are analyzed. © The Authors, published by EDP Sciences, 2017.

We present an original experimental study of the slow compaction dynamics for two- dimensional isotropic granular systems. Compaction dynamics is measured at three different scales : the macroscopic scale through the normalized packing fraction ˜ ρ, the mesoscopic scale through the normalized fraction ˜ φ of domains ideally ordered in the system, and the microscopic scale through the grain mobility μ. The domains ideally ordered are found to obey a growth process dominated by the displacement of domain boundaries. We present also preliminary results of three-dimensional simulations with a model of contact dynamics. These results allow to discuss the difference between the two-dimensional and the three-dimensional cases.

Compared to ideal dry granular materials made of perfectly spherical particles, cohesive granular materials flow in a completely different way. We highlight the major features of this specific flow by investigating the effect of cohesion on the flow of granular materials using numerical simulations. We combine a widely-used Discrete Element Method (DEM) with a simplified model of cohesion (i.e. intermediate-range attraction between particles) to reproduce the dynamics of cohesive granular materials in a 2D rotating drum. The resulting flow is analyzed in light of previous experimental and numerical studies in order to validate and calibrate our model. We retrieve the characteristic intermittent flow in avalanches, called plug-flow. We perform a full analysis of the aggregates of particles flowing along the grain-air interface by measuring the velocity profiles, the dynamic angle of repose and by introducing a novel measurement of surface fluctuations. This latter measurement allows us to characterize the size of the aggregates. We show that this measurement could potentially provide the cohesive powders’ microscopic properties in any field of application.

We carry out density functional theory (DFT) calculations to explore the antiferromagnetic (AFM) spin cycloid in multiferroic BiFeO3 of the R3c ground state structure. We calculate the energy dispersion E(q) of cycloidal spin spirals along the high symmetry directions of the pseudo-cubic unit cell and find a flat AFM spin spiral (or cycloid) ground state with a periodicity of ∼80 nm, which is in good agreement with experiments. To investigate which structural distortion of the R3c phase is the driving mechanism for the stabilization of this cycloid, we further study three artificial phases: cubic, R3c, and R3m. In all cases, we find a large exchange frustration. The comparison between these phases provides detailed insight about how polarization and octahedral antiphase tilting affect the different magnetic interactions and the magnetic ground state in BiFeO3. In R3c BiFeO3, the magnetic ground state is driven by a competition between the frustrated exchange stemming from the hybridization between the elements Bi, Fe, O and the Dzyaloshinskii-Moriya (DM) interaction due to the Fe-Bi ferroelectric displacement. The cycloid appears to be stable because the anisotropy energy in R3c BiFeO3 is relatively small to enforce a collinear order.

We present an unexpectedly strong influence of the proximity effect between the bulk Ru(0001) superconductor and atomically thin layers of Co on the crystal structure of the latter. The Co monolayer grows in two different modifications, such as hcp stacking and a reconstructed ϵ-like phase. While hcp islands show a weak proximity effect on Co and a little suppression of superconductivity in the substrate next to it, the more complex ϵ-like stacking becomes almost fully superconducting. We explain the weak proximity effect between Ru and hcp Co and the rather abrupt jump of the superconducting order parameter by a low transparency of the interface. In contrast, the strong proximity effect without a jump of the order parameter in the ϵ-like phase indicates a highly transparent interface. This work highlights that the proximity effect between a superconductor and a normal metal strongly depends on the crystal structure of the interface, which allows to engineer the proximity effect in hybrid structures.

Transition metal dihalides have recently garnered interest in the context of two-dimensional van der Waals magnets as their underlying geometrically frustrated triangular lattice leads to interesting competing exchange interactions. In particular, NiI2 is a magnetic semiconductor that has been long known for its exotic helimagnetism in the bulk. Recent experiments have shown that the helimagnetic state survives down to the monolayer limit with a layer-dependent magnetic transition temperature that suggests a relevant role of the interlayer coupling. Here, we explore the effects of hydrostatic pressure as a means to enhance this interlayer exchange and ultimately tune the electronic and magnetic response of NiI2. We study first the evolution of the structural parameters as a function of external pressure using first-principles calculations combined with x-ray diffraction measurements. We then examine the evolution of the electronic structure and magnetic exchange interactions via first-principles calculations and Monte Carlo simulations. We find that the leading interlayer coupling is an antiferromagnetic second-nearest-neighbor interaction that increases monotonically with pressure. The ratio between isotropic third- and first-nearest-neighbor intralayer exchanges, which controls the magnetic frustration and determines the magnetic propagation vector q of the helimagnetic ground state, is also enhanced by pressure. As a consequence, our Monte Carlo simulations show a monotonic increase in the magnetic transition temperature, indicating that pressure is an effective means to tune the magnetic response of NiI2.

Magnetic rare-earth orthoferrites RFeO3 host a variety of functional properties from multiferroicity and strong magnetostriction to spin-reorientation transitions and ultrafast light-driven manipulation of magnetism, which can be exploited in spintronics and next-generation devices. Among these systems, SmFeO3 is attracting particular interest for its rich phase diagram and the high temperature Fe-spin magnetic transitions, which combines with a very low temperature and as yet unclear Sm-spin ordering. Various experiments suggest that the interaction between the Sm and Fe magnetic moments (further supported by the magnetic anisotropy), is at the origin of the complex cascade of transitions, but a conclusive and clear picture has not yet been reached. In this paper, by means of comprehensive first-principles calculations, we unravel the role of the magnetic Sm ions in the Fe-spin reorientation transition and in the detected anomalies in the lattice vibrational spectrum, which are a signature of a relevant spin-phonon coupling. By including both Sm-f electrons and noncollinear magnetism, we find frustrated and anisotropic Sm interactions, and a large magnetocrystalline anisotropy mediated by the SOC of the Sm-4f electrons, which drive the complex magnetic properties and phase diagram of SmFeO3.

We have studied the sintering parameters of YBa2Cu3O7-x (YBCO) coatings produced by electrophoretic deposition (EPD) on Ag and Ni substrates. The maximal sintering temperature is ~ 930°C due to partial melting and chemical contamination for Ag and Ni substrates respectively. Increasing the sintering duration does not improve significantly the densification. When Ar sintering atmosphere is used, the coating density is strongly increased on Ag substrates while adhesion is poor on Ni substrates. The Ar-sintered YBCO coating deposited on planar Ag substrate displays a significant magnetic shielding effect for low frequency applied magnetic induction.

Nb2xV2 - 2xO5 (0 <= x <= 1) powders were prepared by a synthetic route based on the inorganic polymerization of alkoxy-choride precursors and characterized by a combination of X-ray diffraction V-51 and Nb-93 NMR and Raman spectroscopy. Amorphous mesoporous thin films of similar compositions were successfully prepared by a modified Evaporation Induced Self Assembly method using polystyrene-b-polyethyleneoxide diblock copolymer as structuring agent. The electrochemical properties of the mesoporous films upon lithium insertion-deinsertion are investigated by cyclic voltammetry. This study highlights the advantages of such nanoarchitecture in terms of increased capacity to insert lithium. (C) 2009 Elsevier B.V. All rights reserved.

The lithium battery electrode compound Li4Ti5O12 was synthesized by calcination of precursor powders obtained through spray-drying of solutions prepared with titanium isopropoxide and lithium nitrate. X-ray diffraction and thermal analysis coupled to mass spectrometry show that single phase crystalline Li4Ti5O12 particles can be obtained after calcination at 800 °C for 2 hours. Decreasing the solution concentration leads to smaller particle sizes but also to an unexpected decrease of the electrochemical capacity, probably related to the presence of residual Li2TiO3. On the contrary, the capacity of the Li4Ti5O12 powder prepared with the high concentration solution can be increased from 150 mAh/g to 165 mAh/g (C/4 rate) by grinding. These results highlight the fact that smaller particles do not systematically display better performances for Li+ intercalation/desintercalation and confirm the need for a comprehensive approach including parameters such as crystallinity, phase purity or agglomeration.

The deformation of hemispherical bubbles under vertical static electric fields was studied using a plane capacitor. The deformation and the bubbles shape have been monitored according to the amplitude of the electric field and the initial volume of the bubbles. Two different substrates, a dry solid plate or a liquid pool, were used to inspect the influence of the pining of the contact line. The deformation of sessile (on dry solid plate) and floating (on a liquid pool) bubbles were compared. The deformation parameter has been rationalized using a simple model. More precisely, the number of interfaces has been found to be a relevant parameter that imposes the shape of the bubbles.

The deformation of hemispherical sessile bubbles made of ferrofluid soap under vertical uniform magnetic fields was studied using Helmholtz coils. The deformation and the bubbles shape were monitored according to...

Driven granular gases present rich dynamical behaviors. Due to inelastic collisions, particles may form dense and slow regions. These clusters emerge naturally during a cooling phenomenon but another dynamical clustering is observed when the system is continuously excited. In this paper, the physical processes that trigger the transition from a granular gas to a dynamical cluster are evidenced through numerical simulations. At the granular scale, the transition is evidenced by the observation of caging effects. At the scale of the system, the transition is emphasized by density fluctuations. Physical arguments, based on relaxation times, provide an analytical prediction for the edge between dynamical regimes.

Strongly driven granular media are known to undergo a transition from a gas-like to a cluster regime when the density of particles is increased. However, the main mechanism triggering this transition is not fully understood so far. Here, we investigate experimentally this transition within a 3D cell filled with beads that are driven by two face-to-face vibrating pistons in low gravity during parabolic flight campaigns. By varying large ranges of parameters, we obtain the full phase diagram of the dynamical regimes reached by the out-of-equilibrium system: gas, cluster or bouncing aggregate. The images of the cell recorded by two perpendicular cameras are processed to obtain the profiles of particle density along the vibration axis of the cell. A statistical test is then performed on these distributions to determinate which regime is reached by the system. The experimental results are found in very good agreement with theoretical models for the gas-cluster transition and for the emergence of the bouncing state. The transition is shown to occur when the typical propagation time needed to transmit the kinetic energy from one piston to the other is of the order of the relaxation time due to dissipative collisions.

Space exploration and exploitation face a major challenge: the handling of granular materials in low-gravity environments. Indeed, grains behave quite differently in space than on Earth, and the dissipative nature of the collisions between solid particles leads to clustering. Within poly-disperse materials, the question of segregation is highly relevant but has not been addressed so far in microgravity. From parabolic flight experiments on dilute binary granular media, we show that clustering can trigger a segregation mechanism, and we observe, for the first time, the formation of layered structures in the bulk.

Granular multiparticle ensembles are of interest from fundamental statistical viewpoints as well as for the understanding of collective processes in industry and in nature. Extraction of physical data from optical observations of three-dimensional (3D) granular ensembles poses considerable problems. Particle-based tracking is possible only at low volume fractions, not in clusters. We apply shadow- based and feature-tracking methods to analyze the dynamics of granular gases in a container with vibrating side walls under microgravity. In order to validate the reliability of these optical analysis methods, we perform numerical simulations of ensembles similar to the experiment. The simulation output is graphically rendered to mimic the experimentally obtained images. We validate the output of the optical analysis methods on the basis of this ground truth information. This approach provides insight in two interconnected problems: the confirmation of the accuracy of the simulations and the test of the applicability of the visual analysis. The proposed approach can be used for further investigations of dynamical properties of such media, including the granular Leidenfrost effect, granular cooling, and gas-clustering transitions.

We investigated experimentally and theoretically the dynamics of a driven granular gas on a square lattice and discovered two characteristic regimes: Initially, given the dissipative nature of the collisions, particles move erratically through the system and start to gather on selected sites called traps. Later on, the formation of those traps leads to a strong decrease of the grain mobility and slows down dramatically the dynamics of the entire system. We realize detailed measurements linking a trap’s stability to the global evolution of the system and propose a model reproducing the entire dynamics of the system. Our work emphasizes the complexity of coarsening dynamics of dilute granular systems.

Neodymium spherical magnets are inexpensive objects that demonstrate how dipolar particles self-assemble into various structures ranging from 1D chains to 3D crystals. Assemblies of these magnets are nicknamed magnetostructures and this paper focuses on a variety called magnetotubes, which are some curved square lattices forming cylinders. We experimentally and numerically observe that such magnetotubes can self-buckle, above a critical aspect ratio. In fact, the underlying dipolar ordering of such structures is found to exhibit a collective reorganization, altering the mechanical stability of the entire system. We identify the conditions in which these phenomena occur, and we emphasize that metastable states coexist. This suggests that a wide variety of magnetostructures, including chains and magnetocrystals, may collapse due to the coexistence of multiple ground states and global reorientation of dipoles.

We perform three-dimensional particle-based simulations of confined, vibrated, and magnetizable beads to study the effect of cell geometry on pattern selection. For quasi-two-dimensional systems, we reproduce previously observed macroscopic patterns such as hexagonal crystals and labyrinthine structures. For systems at the crossover from two to three dimensions, labyrinthine branches shorten and are replaced by triplets of beads forming upright triangles which self-organize into a herringbone pattern. This transition is associated with increases in both translational and orientational orders.

In microgravity, the successive inelastic collisions in a granular gas can lead to a dynamical clustering of the particles. This transition depends on the filling fraction of the system, the restitution of the used materials and on the size of the particles. We report simulations of driven bi-disperse gas made of small and large spheres. The size as well as the mass difference imply a strong modification in the kinematic chain of collisions and therefore alter significantly the formation of a cluster. Moreover, the different dynamical behaviors can also lead to a demixing of the system, adding a few small particles in a gas of large ones can lead to a partial clustering of the taller type. We realized a detailed phase diagram recovering the encountered regimes and developed a theoretical model predicting the possibility of dynamical clustering in binary systems.

We numerically and theoretically investigate the behavior of a granular gas driven by asymmetric plates. The injection of energy in the dissipative system differs from one side to the opposite one. We prove that the dynamical clustering which is expected for such a system is affected by the asymmetry. As a consequence, the cluster position can be fully controlled. This property could lead to various applications in the handling of granular materials in low-gravity environment. Moreover, the dynamical cluster is characterized by natural oscillations which are also captured by a model. These oscillations are mainly related to the cluster size, thus providing an original way to probe the clustering behavior.

In microgravity, the gathering of granular material can be achieved by a dynamical clustering whose existence depends on the geometry of the cell that contains the particles and the energy that is injected into the system. By compartmentalizing the cell in several subcells of smaller volume, local clustering is triggered and the so formed dense regions act as stable traps. In this paper, molecular dynamics simulations were performed in order to reproduce the phenomenon and to analyze the formation and the stability of such traps. Depending on the total number N of particles present in the whole system, several clustering modes are encountered and a corresponding bifurcation diagram is presented. Moreover, an iterative model based on the measured particle flux F as well as a theoretical model giving the asymptotical steady states are used to validate our results. The obtained results are promising and can provide ways to manipulate grains in microgravity.

We investigate numerically and theoretically the internal structures of a driven granular gas in cuboidal cell geometries. Clustering is reported and particles are classified as gaseous or clustered via a local packing fraction criterion based on a Voronoi tessellation. We observe that small clusters arise in the corners of the box, elucidating early reports of partial clustering. These aggregates have a condensation-like surface growth. When a critical size is reached, a structural transition occurs and all clusters merge together, leaving a hole in the center of the cell. This hole then becomes the new center of particle capture. Taking into account all structural modifications and defining a saturation packing fraction, we propose an empirical model for the cluster growth.

We study experimentally the dynamical behavior of few large tracer particles placed in a quasi-2D granular “gas” made of many small beads in a low-gravity environment. Multiple inelastic collisions transfer momentum from the uniaxially driven gas to the tracers whose velocity distributions are studied through particle tracking. Analyzing these distributions for an increasing system density reveals that translational energy equipartition is reached at the onset of the gas-liquid granular transition corresponding to the emergence of local clusters. The dynamics of a few tracer particles thus appears as a simple and accurate tool to detect this transition. A model is proposed for describing accurately the formation of local heterogeneities.

A new experimental facility has been designed and constructed to study driven granular media in a low-gravity environment. This versatile instrument, fully automatized, with a modular design based on several interchangeable experimental cells, allows us to investigate research topics ranging from dilute to dense regimes of granular media such as granular gas, segregation, convection, sound propagation, jamming, and rheology - all without the disturbance by gravitational stresses active on Earth. Here, we present the main parameters, protocols, and performance characteristics of the instrument. The current scientific objectives are then briefly described and, as a proof of concept, some first selected results obtained in low gravity during parabolic flight campaigns are presented. © 2018 Author(s).

Partitioning space into polyhedra with a minimum total surface area is a fundamental question in science and mathematics. In 1887, Lord Kelvin conjectured that the optimal partition of space is obtained with a 14-faced space-filling polyhedron, called tetrakaidecahedron. Kelvin’s conjecture resisted a century until Weaire and Phelan proposed in 1994 a new structure, made of eight polyhedra, obtained from numerical simulations. Herein, we propose a stochastic method for finding efficient polyhedral structures, maximizing the mean isoperimeter Q, instead of minimizing total area. We show that novel optimal structures emerge with non-equal cell volumes and uncurved facets. A partition made of 24 polyhedra, is found to surpass the previous known structures. Our work suggests that other structures with high isoperimeter values are still to be discovered in the pursuit of optimal space partitions.

We use first-principles calculations to understand the behavior of the Seebeck coefficient (S) in Bi2Te3 as a function of isotropic pressure. We perform calculations up to 5 GPa using density functional theory and with thermoelectric properties extracted using Boltzmann transport equations. We find that with the increase in pressure the system becomes more metallic, in agreement with previous calculations on Sb2Te3. For p-type doping the overall behavior is a decrease in S with an increase in pressure. At small values of hole doping (p=1.8×1018cm-3), we obtain an anomalous variation of S under 2 GPa, which is an indication of the electronic topological transition. For n-type doping, S slightly increases with pressure. © 2014 American Physical Society.

Abstract Outstanding photovoltaic (PV) materials combine a set of advantageous properties including large optical absorption and high charge carrier mobility, facilitated by small effective masses. Halide perovskites (ABX3, where X = I, Br, or Cl) are among the most promising PV materials. Their optoelectronic properties are governed by the BX bond, which is responsible for the pronounced optical absorption and the small effective masses of the charge carriers. These properties are frequently attributed to the ns2 configuration of the B atom, i.e., Pb 6s2 or Sn 5s2 (“lone-pair”) states. The analysis of the PV properties in conjunction with a quantum-chemical bond analysis reveals a different scenario. The BX bond differs significantly from ionic, metallic, or conventional 2c2e covalent bonds. Instead it is better regarded as metavalent, since it shares about one p-electron between adjacent atoms. The resulting σ-bond, formally a 2c1e bond, is half-filled, causing pronounced optical absorption. Electron transfer between B and X atoms and lattice distortions open a moderate bandgap resulting in charge carriers with small effective masses. Hence, metavalent bonding explains favorable PV properties of halide perovskites, as summarized in a map for different bond types, which provides a blueprint to design PV materials.

We have studied foaming dynamics in Hele-Shaw cells partially filled with a soap and water mixture. A series of upside-down flips produces an intermittent wetting of the cell and leads to foam formation. As a function of the number of flips, an increasing number of bubbles composes the foam, until saturation is observed. Statistical analysis shows that the bubble size follows a Gamma distribution. Contrary to common belief, this foaming dynamics by "shaking" creates homogeneous foam, even though the system may pass through transient heterogeneous configurations. A mechanistic interpretation is proposed and included into a theoretical model.

An experimental study of a granular surface submitted to a circular fluid motion is presented. The appearance of an instability along the sand-water interface is observed beyond a critical radius r(c). This creates ripples with a spiral shape on the granular surface. A phase diagram of such patterns is constructed and discussed as a function of the rotation speed omega of the flow and as a function of the height of water h above the surface. The study of r(c) as a function of h, omega, and r parameters is reported. Thereafter, r(c) is shown to depend on the rotation speed according to a power law. The ripple wavelength is found to decrease when the rotation speed increases and is proportional to the radial distance r. The azimuthal angle epsilon of the spiral arms is studied. It is found that epsilon scales with homegar. This lead to the conclusion that epsilon depends on the fluid momentum. Comparison with experiments performed with fluids allows us to state that the spiral patterns are not the signature of an instability of the boundary layer.

We have experimentally investigated 2-dimensional dense bubble flows underneath inclined planes. Velocity profiles and velocity fluctuations have been measured. A broad second-order phase transition between two dynamical regimes is observed as a function of the tilt angle theta. For low theta values, a block motion is observed. For high theta values, the velocity pro. le becomes curved and a shear velocity gradient appears in the flow.

An experimental study of a binary granular mixture submitted to a transient shear flow in a cylindrical container is reported. The formation of ripples with a spiral shape is observed. The appearance of phase segregation in those spiral patterns is shown. The relative grain size between sand species is found to be a relevant parameter leading to phase segregation. However, the relative repose angle is an irrelevant parameter. The formation of sedimentary structures is also presented. They result from a ripple climbing process. The "sub-critical" or "super-critical" character of the lamination patterns is shown to depend on the rotation speed of the container. (C) 2002 Elsevier Science B.V. All rights reserved.

This paper reports on an experimental study of the splitting instability of an air bubble a few centimetres in diameter placed in a sealed cylindrical cell filled with liquid and submitted to vertical oscillations. The response of the bubble to the oscillations is observed with a high-speed video camera. It is found that the bubble dynamics is closely associated with the acceleration of the cell Gamma. For small acceleration values, the bubble undergoes minor shape deformations. With increasing acceleration values, these deformations are amplified and for sufficiently large Gamma the bubble becomes toroidal. The bubble may then become unstable and split into smaller parts. The onset of bubble division is studied and its dependency on physical parameters such as the fluid viscosity, the fluid surface tension and the initial size of the bubble is presented. It is found that the criterion for the bubble splitting process is associated with a threshold based on the acceleration of the oscillations. Above this threshold, the number of bubbles present in the cell is observed to grow until a final steady state is reached. Data analysis reveals that the final bubble size may be characterized in terms of Bond number.

We report an experimental study of aqueous foam imbibition in microgravity with strict mass conservation. The foam is in a Hele-Shaw cell. The bubble edge width l is measured by image analysis. The penetration of the liquid in the foam, the foam imbibition, the foam inflation, and the rigidity loss are shown all to obey strict diffusion processes. The motion of bubbles needed for the foam inflation is a slow two-dimensional process with respect to the one-dimensional capillary rise of liquid. The foam is found to imbibes faster than it inflates.

Coming from the framework of unmarked fry tracking, we compared the capacities, advantages, and disadvantages of two recent video tracking systems: EthoVision 2.3 and a new prototype of multitracking. The EthoVision system has proved to be impressive for tracking a fry using the detection by gray scaling. Detection by subtraction has given less accurate results. Our video multitracking system is able to detect and track more than 100 unmarked fish by gray scaling technique. It permits an analysis at the group level as well as at the individual level. The multitracking program is able to attribute a number to each fish and to follow each one for the whole duration of the track. Our system permits the analysis of the movement of each individual, even if the trajectories of two fish cross each other. This is possible thanks to the theoretical estimation of the trajectory of each fish, which can be compared with the real trajectory (analysis with feedback). However, the period of the track is limited for our system (about 1 min), whereas EthoVision is able to track for numerous hours. In spite of these limitations, these two systems allow an almost continuous automatic sampling of the movement behaviors during the track.

We have performed experiments of axial segregation in the Oyama's drum. We have tested binary granular mixtures during very long times. The segregation patterns have been captured by a CCD camera and spatio-temporal graphs are created. We report the occurrence of instabilities which can last several hours! We stress that those instabilities originate from the competition between axial and radial segregations. We put into evidence the occurrence of giant fluctuations in the fraction of grain species along the surface during the unstable periods. (C) 2003 Elsevier B.V. All rights reserved.

The motion of liquid into a foam under low-gravity conditions is studied both experimentally and theoretically. The foam is confined to two dimensions in a Hele-Shaw cell and the liquid fraction measured by image analysis. The foam imbibition is shown to be a diffusive process. Two models are analysed, corresponding to the limits of rigid and mobile interfaces in the Plateau borders. Liquid fraction profiles are compared to experimental ones. (c) 2004 Elsevier B.V. All rights reserved.

The authors have generated two-dimensional foams by imposing an intermittent drainage in a Hele-Shaw cell partially filled with a detergent/water mixture. The foam generation associated with this process is reproducible and depends on the surfactant molecules composing the solution. A kinetic model can be proposed for the foam evolution. The structure of the foam is also investigated: the average bubble side number and correlation functions are measured. Distinguishable behaviors are observed for different surfactant molecules. This way of producing a foam is thus adequate for applied foam structure characterizations and fundamental studies. (c) 2007 American Institute of Physics.

We extend the density functional perturbation theory formalism to the case of noncollinear magnetism. The main problem comes with the exchange-correlation (XC) potential derivatives, which are the only ones that are affected by the noncollinearity of the system. Most of the present XC functionals are constructed at the collinear level, such that the off-diagonal (containing magnetization densities along x and y directions) derivatives cannot be calculated simply in the noncollinear framework. To solve this problem, we consider here possibilities to transform the noncollinear XC derivatives to a local collinear basis, where the z axis is aligned with the local magnetization at each point. The two methods we explore are (i) expanding the spin rotation matrix as a Taylor series and (ii) evaluating explicitly the XC for the local density approximation through an analytical expression of the expansion terms. We compare the two methods and describe their practical implementation. We show their application for atomic displacement and electric field perturbations at the second order, within the norm- conserving pseudopotential methods.

In this work, first-principles calculations of Cu2ZnSnS4, Cu2ZnGeS4 and Cu2ZnSiS4 are per- formed to highlight the impact of the cationic substitution on the structural, electronic and optical properties of kesterite compounds. Direct bandgaps are reported with values of 1.32, 1.89 and 3.06 eV respectively for Cu2ZnSnS4, Cu2ZnGeS4 and Cu2ZnSiS4 and absorption coefficients of the order of 10^4 cm−1 are obtained, indicating the applicability of these materials as absorber layer for solar cell applications. In the second part of this study, ab initio results are used as input data to model the electrical power conversion efficiency of kesterite-based solar cells. In that perspective, we used an improved version of the Shockley-Queisser model including non-radiative recombination via an external parameter defined as the internal quantum efficiency. Based on predicted optimal absorber layer thicknesses, the variation of the solar cell maximal efficiency is studied as a function of the non-radiative recombination rate. Maximal efficiencies of 25.71, 19.85 and 3.10 % are reported respectively for Cu2ZnSnS4, Cu2ZnGeS4 and Cu2ZnSiS4 for vanishing non-radiative recombination rate. Using an internal quantum efficiency value providing experimentally comparable VOC values, cell efficiencies of 15.88, 14.98 and 2.66 % are reported respectively for Cu2ZnSnS4, Cu2ZnGeS4 and Cu2ZnSiS4. We confirm the suitability of Cu2ZnSnS4 in single junction solar cells, with a possible efficiency improvement of nearly 10% enabled through the reduction of the non-radiative recombination rate. In addition, Cu2ZnGeS4 appears to be an interesting candidate as top cell absorber layer for tandem approaches whereas Cu2ZnSiS4 might be interesting for transparent photovoltaic windows.

To reduce the prominent VOC-deficit that limits kesterite-based solar cells efficiencies, Ge has been proposed over the recent years with encouraging results as the reduction of the non-radiative recombination rate is considered as a way to improve the well-known Sn-kesterite world record efficiency. To gain further insight into this mechanism, we investigate the physical behaviour of intrinsic point defects both upon Ge doping and alloying of Cu2ZnSnS4 kesterite. Using a first-principles approach, we confirm the p-type conductivity of both Cu2ZnSnS4 and Cu2ZnGeS4, attributed to the low formation energies of the VCu and CuZn acceptor defects within the whole stable phase diagram range. Via doping of the Sn-kesterite matrix, we report the lowest formation energy for the substitutional defect GeSn. We also confirm the detrimental role of the substitutional defects XZn (X=Sn,Ge) acting as recombination centres within the Sn-based, the Ge-doped and the Ge-based kesterite. Upon Ge incorporation, we highlight, along with the increase of the XZn (X=Sn,Ge) neutral defect formation energy, the reduction of the lattice distortion resulting in the reduction of the carrier capture cross section. Both of these elements leading to a decrease of the non-radiative recombination rate within the bulk material following the Sn substitution by Ge.

We refute in this Reply the criticisms made by Abdel-Aty. We show that none of them are founded and we demonstrate very explicitly what is wrong with the arguments developed by this author.

When some of the parties of a multipartite entangled pure state are lost, the question arises whether the residual mixed state is also entangled, in which case the initial entangled pure state is said to be robust against particle loss. In this paper, we investigate this entanglement robustness for N-qubit pure states. We identify exhaustively all entangled states that are fragile, i.e., not robust, with respect to the loss of any single qubit of the system. We also study the entanglement robustness properties of symmetric states and put these properties in the perspective of the classification of states with respect to stochastic local operations assisted with classic communication (SLOCC classification).

In a recent work, we provided a standardized and exact analytical formalism for computing in the semiclassical and asymptotic regime, the radiation force experienced by a two-level atom interacting with any number of plane waves with arbitrary intensities, frequencies, phases, and propagation directions [J. Opt. Soc. Am. B 35, 127 (2018)]. Here, we extend this treatment to the multilevel atom case, where degeneracy of the atomic levels is considered and polarization of light enters into play. A matrix formalism is developed to this aim.

The transmission probability of ultracold atoms through a micromaser is studied in the general case where a detuning between the cavity mode and the atomic transition frequencies is present. We generalize previous results established in the resonant case (zero detuning) for the mesa mode function. In particular, it is shown that the velocity selection of cold atoms passing through the micromaser can be very easily tuned and enhanced using a non-resonant field inside the cavity. Also, the transmission probability exhibits with respect to the detuning very sharp resonances that could define single cavity devices for high accuracy metrology purposes (atomic clocks).

In a recent work, Abdel-Aty and Obada (2002 J. Phys. B: At. Mol. Opt. Phys. 35 807-13) analysed the quantum inversion of cold atoms in a microcavity, the motion of the atoms being described quantum mechanically. Two-level atoms were assumed to interact with a single mode of the cavity, and the off-resonance case was considered (namely the atomic transition frequency is detuned from the single-mode cavity frequency). We demonstrate in this paper that this case is incorrectly treated by these authors, and we therefore question their conclusions.

We analyze the quantum theory of the two-mode micromaser pumped by cold three-level atoms with a Lambda-configuration under the two-photon resonance condition. We focus more specifically on the large detuning limit where the detuning between the two cavity mode frequencies and the two atomic transition frequencies is large in comparison with the atom-cavity coupling constants. We show that this regime can mimic a virtual two-level atom micromaser without spontaneous emission where the cavity acts for the atoms as a potential barrier or a potential well (depending on the sign of the detuning) and a zero potential but no more both as a potential barrier and a potential well as it is the case for the usual cold two-level atom micromaser [M. O. Scully, G. M. Meyer, and H. Walther, Phys. Rev. Lett. 76, 4144 (1996)]. This introduces interesting options for engineering the interaction between the cold atoms and the cavity. The elimination of the spontaneous emission solves a major issue of the conventional cold two-level atom micromaser as the transit time of cold atoms inside and in the vicinity of the cavity is usually much larger than the atomic level lifetimes. It is also shown that the cold atom regime is very sensitive to the sign of the detuning (in contrast to the hot atom regime) and that, according to this sign, the cavity may speed up or slow down the incident three-level atoms after their interaction with the field.

We propose a detailed study of the geometric entanglement properties of pure symmetric N-qubit states, focusing more particularly on the identification of symmetric states with a high geometric entanglement and how their entanglement behaves asymptotically for large N. We show that much higher geometric entanglement with improved asymptotical behavior can be obtained in comparison with the highly entangled balanced Dicke states studied previously. We also derive an upper bound for the geometric measure of entanglement of symmetric states. The connection with the quantumness of a state is discussed.

The quantum theory of the cold-atom micromaser including the effects of gravity is considered. We show that gravity does not break the special properties of the induced emission probability for the micromaser in the cold atom regime and rather new effects are predicted. In particular, we show that the cavity acts in the gravity field as an additional repulsive and attractive potential, resulting in quasibound states of the atomic motion. This feature gives rise to fine resonances in the induced emission probability that are not restricted to any particular cavity mode function, in contrast to the usual cold-atom micromaser. It is also shown that the atom is able to emit a photon inside the cavity, though classically it does not reach the interaction region. Predictions about the photon number statistics when the cavity is pumped by a flux of excited atoms are finally given. Unusual highly nonclassical "dragon" distributions are still predicted in the vertical geometry. (c) 2005 American Institute of Physics.

We propose a generalization of the Bloch sphere representation for arbitrary spin states. It provides a compact and elegant representation of spin density matrices in terms of tensors that share the most important properties of Bloch vectors. Our representation, based on covariant matrices introduced by Weinberg in the context of quantum field theory, allows for a simple parametrization of coherent spin states, and a straightforward transformation of density matrices under local unitary and partial tracing operations. It enables us to provide a criterion for anticoherence, relevant in a broader context such as quantum polarization of light.

The quantum theory of the mazer in the nonresonant case (a detuning between the cavity mode and the atomic transition frequencies is present) is described. The generalization from the resonant case is far from being direct. Interesting effects of the mazer physics are pointed out. In particular, it is shown that the cavity may slow down or speed up the atoms according to the sign of the detuning and that the induced emission process may be completely blocked by use of a positive detuning. It is also shown that the detuning adds a potential step effect not present at resonance and that the use of positive detunings defines a well-controlled cooling mechanism. In the special case of a mesa cavity mode function, generalized expressions for the reflection and transmission coefficients have been obtained. The general properties of the induced emission probability are finally discussed in the hot, intermediate, and cold atom regimes. Comparison with the resonant case is given.

We propose a technique to obtain subwavelength resolution in quantum imaging with potentially 100% contrast using incoherent light. Our method requires neither path-entangled number states nor multiphoton absorption. The scheme makes use of N photons spontaneously emitted by N atoms and registered by N detectors. It is shown that for coincident detection at particular detector positions a resolution of lambda/N can be achieved.

We present a comprehensive study of maximally entangled symmetric states of arbitrary numbers of qubits in the sense of the maximal mixedness of the one-qubit reduced density operator. A general criterion is provided to easily identify whether given symmetric states are maximally entangled in that respect or not. We show that these maximally entangled symmetric (MES) states are the only symmetric states for which the expectation value of the associated collective spin of the system vanishes, as well as in corollary the dipole moment of the Husimi function. We establish the link between this kind of maximal entanglement, the anticoherence properties of spin states, and the degree of polarization of light fields. We analyze the relationship between the MES states and the classes of states equivalent through stochastic local operations with classical communication (SLOCC). We provide a nonexistence criterion of MES states within SLOCC classes of qubit states and show in particular that the symmetric Dicke state SLOCC classes never contain such MES states, with the only exception of the balanced Dicke state class for even numbers of qubits. The 4-qubit system is analyzed exhaustively and all MES states of this system are identified and characterized. Finally the entanglement content of MES states is analyzed with respect to the geometric and barycentric measures of entanglement, as well as to the generalized N-tangle. We show that the geometric entanglement of MES states is ensured to be larger than or equal to 1/2, but also that MES states are not in general the symmetric states that maximize the investigated entanglement measures.

The quantum theory of the cold atom micromaser including the effects of gravity is established in the general case where the cavity mode and the atomic transition frequencies are detuned.We show that atoms which classically would not reach the interaction region are able to emit a photon inside the cavity. The system turns out to be extremely sensitive to the detuning and in particular to its sign. A method to solve the equations of motion for non resonant atom-field interaction and arbitrary cavity modes is presented.

A short review of the theoretical studies of the cold atom micromaser (mazer) is presented. Existing models are then improved by considering more general working conditions. Especially, the mazer physics is investigated in the situation where a detuning between the cavity mode and the atomic transition frequency is present. Interesting new effects are pointed out. Especially, it is shown that the cavity may slow down or speed up the atoms according to the sign of the detuning and that the induced emission process may be completely blocked by use of a positive detuning. The transmission probability of ultracold atoms through a micromaser is also studied and we generalize previous results established in the resonant case. In particular, it is shown that the velocity selection of cold atoms passing through the micromaser can be very easily tuned and enhanced using a nonresonant field inside the cavity.

Athermal two-dimensional granular systems are exposed to external mechanical noise leading to Brownian-like motion. Using tunable repulsive interparticle interaction, it is shown that the same microstructure as that observed in colloidal suspensions can be quantitatively recovered at a macroscopic scale. To that end, experiments on granular and colloidal systems made up of magnetized particles as well as computer simulations are performed and compared. Excellent agreement throughout the range of the magnetic coupling parameter Γ is found for the pair distribution as well as the bond-orientational correlation functions. This finding opens new ways to efficiently and very conveniently explore phase transitions, crystallization, nucleation, etc in confined geometries.

An original experiment is introduced that allows students to relate the Brownian motion of a set of superparamagnetic colloidal particles to their macroscopic diffusion. An external and constant magnetic field is first applied to the colloidal suspension so that the particles self-organize into chains. When the magnetic field is removed, the particles then freely diffuse from their positions in the chain, starting from the same coordinate on the axis perpendicular to the initial chain. This configuration thus enables an observer to study the one dimensional diffusion process, while also observing the underlying Brownian motion of the microscopic particles. Moreover, by studying the evolution of the particle distribution, a measurement of the diffusion coefficient can be obtained. In addition, by repeating this measurement with fluids of various viscosities, the Stokes-Einstein relation may be illustrated.

The packing fraction dynamics of a wet granular material submitted to freeze-thaw cycling is investigated experimentally. The dynamics is strongly influenced by the liquid volume fraction ω in the considered range of 0.03<ω<0.32. This range of liquid contents covers different regimes of wetness from the creation of the capillary network until the formation of large clusters and finally close to the saturated case. For the liquid contents ω0.15, the pile experiences a decompaction until a particular value of the packing fraction 0.56 corresponding to a random loose packing configuration for monosized spheres. Moreover, the decompaction starts after a cycling number that decreases exponentially with the liquid content. Finally, we show that the packing dynamics can be well modeled on the basis of a Landau potential with an asymmetric double-well structure. The onset of decompaction represents the tendency of the system to stay in a metastable state. After several cycles, the forces induced by the thermal cycling and local stochastic rearrangements of the grains can drive the system to overcome the energy barrier of the cohesive forces. © 2019 American Physical Society.

We present both experimental and numerical investigations of compaction in granular materials composed of rods. As a function of the particles size and with respect to the container diameter, we have observed large variations of the asymptotic packing volume fraction. The relevant parameter is the ratio between the rod length l and the tube diameter D. Even the compaction dynamics remains unchanged for various particle lengths, and a transition between 3d and 2d ordering for grain orientations is observed for l/D= 1. A toy model for the compaction of needles on a lattice is also proposed. This toy model gives a complementary view of our experimental results and leads to behaviors similar to experimental ones.

When ferromagnetic particles are suspended at an interface under magnetic fields, dipole-dipole interactions compete with capillary attraction. This combination of forces has recently given promising results towards controllable self-assemblies as well as low-Reynolds-number swimming systems. The elementary unit of these assemblies is a pair of particles. Although equilibrium properties of this interaction are well described, the dynamics remain unclear. In this paper, the properties of magnetocapillary bonds are determined by probing them with magnetic perturbations. Two deformation modes are evidenced and discussed. These modes exhibit resonances whose frequencies can be detuned to generate nonreciprocal motion. A model is proposed that can become the basis for elaborate collective behaviors.

The flowing properties of 10 lactose powders commonly used in pharmaceutical industries have been analyzed with three recently improved measurement methods. The first method is based on the heap shape measurement. This straightforward measurement method provides two physical parameters (angle of repose αr and static cohesive index σr) allowing to make a first screening of the powder properties. The second method allows to estimate the rheological properties of a powder by analyzing the powder flow in a rotating drum. This more advanced method gives a large set of physical parameters (flowing angle αf, dynamic cohesive index σf, angle of first avalanche αa and powder aeration %ae) leading to deeper interpretations. The third method is an improvement of the classical bulk and tapped density measurements. In addition to the improvement of the measurement precision, the densification dynamics of the powder bulk submitted to taps is analyzed. The link between the macroscopic physical parameters obtained with these methods and the powder granulometry is analyzed. Moreover, the correlations between the different flowability indexes are discussed. Finally, the link between grain shape and flowability is discussed qualitatively.

The extremely slow compaction dynamics of wet granular assemblies is studied experimentally. The cohesion, due to capillary bridges between neighboring grains, is tuned using different liquids having specific surface tension values. The compaction dynamics of a cohesive packing obeys an inverse logarithmic law, like most dry random packings. However, the characteristic relaxation time 􏰌 grows strongly with cohesion. A model, based on free volume kinetic equations and the presence of a capillary energy barrier, is able to reproduce quantitatively the experimental curves.

Abstract.: Ferromagnetic particles are incorporated in a thin soft elastic matrix. A lamella, made of this smart material, is studied experimentally and modeled. We show herein that thin films can be actuated using an external magnetic field applied through the system. The system is found to be switchable since subcritical pitchfork bifurcation is discovered in the beam shape when the magnetic field orientation is modified. Strong magnetoelastic effects can be obtained depending on both field strength and orientation. Our results provide versatile ways to contribute to many applications from the microfabrication of actuators to soft robotics. As an example, we created a small synthetic octopus piloted by an external magnetic field. Graphical abstract: [Figure not available: see fulltext.] © 2017, EDP Sciences, SIF, Springer-Verlag Berlin Heidelberg.

We present an experimental protocol that allows one to tune the packing fraction eta of a random pile of ferromagnetic spheres from a value close to the lower limit of random loose packing eta(RLP) similar or equal to 0.56 to the upper limit of random close packing eta(RCP) similar or equal to 0.64. This broad range of packing fraction values is obtained under normal gravity in air, by adjusting a magnetic cohesion between the grains during the formation of the pile. Attractive and repulsive magnetic interactions are found to affect stongly the internal structure and the stability of sphere packing. After the formation of the pile, the induced cohesion is decreased continuously along a linear decreasing ramp. The controlled collapse of the pile is found to generate various and reproducible values of the random packing fraction eta.

Powder rheology and its sensitivity to surrounding environmental condition by controlling the surface properties of the particles is one of the major challenges of the powder industries. Indeed, handling large quantities needs powders with good flowability, adequate compressibility and few electrostatic charges. We have performed a chemical treatment in order to obtain hydrophobic glass beads and its bulk behavior has been compared with raw glass beads depending on the humidity. We characterized flow properties under different processing equipments. We observed that by performing hydrophobic surface treatment sensitivity of glass beads reduced to the humidity. Furthermore, the influence of the electrostatic charges was an undeniable factor in increasing the viscosity of hydrophobic glass beads and consequently lowering its flowability in front of raw glass beads; at low shear rate. At high shear rate, the powders presented similar behaviors. © 2021 Elsevier B.V.

We study the effect of three types of mesoporous silica (MPS) particles on the flow of three common excipients: microcrystalline cellulose, lactose and maize starch. While MPS are commonly considered as excipient and also as drug delivery carrier, the effects of MPS as flow aid additive and as powder stabilizer are investigated. MPS particles, called additive in the present study, are found to decrease powder cohesiveness, in particular for powders having higher water content and higher initial cohesiveness. According to both particle and pore size of MPS particles, the effect can be immediate (for small MPS particles having small pore size) or on the longer term (for larger MPS particles having higher pore size). Moreover, the electrostatic properties of the blends are modified by the presence of MPS. The quantity of electrostatic charge created in the blends during a flow in contact with stainless steel is decreased by the addition of MPS. We show that this decrease is induced by a modification of electric resistivity. © 2019 Elsevier B.V.

Evaporation of sessile colloidal droplets is a way to organize suspended particles. It is already known that the composition of the surrounding fkuid modi es the dried deposit. For superparamagnetic particles, recent studies showed that external magnetic fi elds can act as remote controls for those deposits. In this paper, we study the confi guration space given by the interplay of such fi elds and a modi cation of the fluid composition by considering various concentrations of phosphate buffered saline (PBS). We show that the magnetic fi eld modifi es the morphological properties of the deposit, while the composition (i.e. PBS concentration) modifi es the density profi le of the deposit. We then present an explanation of these influences considering the competition between (i) sedimentation, (ii) coffee-ring and (iii) Marangoni flows. From these considerations, we propose a master curve which should be able to model the deposit densities of any system where the above mechanisms compete with each other.

This article is a review of our recent and new experimental works on granular compaction. The effects of various microscopic parameters on the compaction dynamics are addressed, in particular the influence of the grain shape, the friction and the cohesion between the grains. Two dimensional and three dimensional systems are analysed. And the role of dimensionality will be emphasized. Theoretical and numerical investigations provide additional informations about that phenomenon. Indeed numerical models permit us to study the influence of some parameters not easily accessible experimentally. Our results show that the above mentioned parameters have a deep impact on the compaction dynamics. Anisotropic grains lead to two different compaction regimes separated by a "burst" of the packing fraction. Friction is observed to modify how the grains are arranged in the pile. This is confirmed by numerical simulations. Cohesive forces between particles inhibit compaction and lead to extremely low values of the packing fraction.

We have experimentally investigated the influence of a magnetic interaction between the grains on the flow of a granular material in a rotating drum.

When identical soft ferromagnetic particles are suspended at some water-air interface, capillary attraction is balanced by magnetic repulsion induced by a vertical magnetic field. By adjusting the magnetic field strength, the equilibrium interdistance between particles can be tuned. The aim of this paper is to study the ordering of particles for large assemblies. We have found an upper size limit above which the assembly collapses due to capillary effects. Before reaching this critical number of particles, defects are always present and limit the perfect ordering expected for that system. This is due to the curvature of the interface induced by the weight of the self-assembly.

Pulmonary drug administration has long been used for local or systemic treatment due to several advantages. Dry powder inhalers emerge as the most promising due to efficiency, ecologic, and drug stability concerns. Coarse lactose-carrier is still the gold standard when inhalation powders are developed. Despite some efforts to produce new types of powders, the lung drug deposition is still poorly controlled, which will ultimately impact therapeutic effectiveness. In this study, we developed “engineered-inhalation powders” using the spray-drying technique. Multiple carbohydrates excipients were binary mixed and combined with two active pharmaceutical ingredients for asthma therapy (budesonide and formoterol). Particle morphology, from spherical to deflated shapes, was characterized by the number and the depth of dimples measured from SEM images. We define a new characteristic deflation ratio ξ as the product between the number of dimples and their depth. Six different powders having opposite morphologies have been selected and we have demonstrated a linear correlation between the fine particle fraction and the deflation ratio of produced powders. Overall, we showed first that the morphology of inhalable powder can be finely tuned by spray-drying technique when excipients varied. Secondly, we developed stable inhalation powders that simultaneously induced high fine particle fractions (>40%) for two drugs due to their deflated surface. The stability has been evaluated for up to 2 months at room temperature.

The flow properties of powders are mainly due to the interplay of cohesive forces and intergrain frictional forces. We have experimentally investigated a "smart granular system" for which the interparticle cohesion can be tuned by a magnetic field B. We show that the rheological features of such a system can be controlled. Indeed, the granular flow can be controlled or even stopped by the magnetic field. Depending on the orientation of B, different dynamical regimes can be obtained like a "dry liquid state" forming conical droplets as well as a "layered soft state". Scaling lows are given for the flow rate outside a funnel as a function of B and for the stopping threshold of the flow as a function of the funnel output diameter D. From this analysis, it appears that the flowing properties are related to the dimensionality of the magnetic aggregates.

The authors have investigated the flow properties of powders by using two classical techniques based on the shear stress measurements and the count of intermittent avalanches, respectively. Results are compared with measurements of the compaction dynamics. Strong correlations are evidenced between compaction relaxation parameters and free flow characteristics. Those correlations are given by semiempirical laws based on physical arguments. This work opens perspectives in powder technology and the knowledge on granular matter. (c) 2006 American Institute of Physics.

While the aggregation process of superparamagnetic colloids in strong magnetic field is well known on short time since a few decades, recent theoretical works predicted an equilibrium state reached after a long time. In the present paper, we present experimental observations of this equilibrium state with a two-dimensional system and we compare our data with the predictions of a pre-existing model. Above a critical aggregation size, a deviation between the model and the experimental data is observed. This deviation is explained by the formation of ribbon-shaped aggregates. The ribbons are formed due to lateral aggregation of chains. An estimation of the magnetic energy for chains and ribbons shows that ribbons are stable structures when the number of magnetic grains is higher than N = 30.

Self-assembly due to capillary forces is a common method for generating 2D mesoscale structures made of identical particles floating at some liquid-air interface. We show herein how to create soft entities that deform or not the liquid interface as a function of the strength of some applied magnetic field. These smart floating objects self-assemble or not depending on the application of an external field. Moreover, we show that the self-assembling process can be reversed opening ways to rearrange structures.

Evaporation of sessile droplets is a method to organize suspended particles on solid substrates. Many studies have demonstrated that Marangoni flows caused by surface adsorbed molecules or temperature gradients can strongly a ect the dried deposit. In the present paper, we show how transitional Marangoni instabilitiy can be triggered by bulk-diluted tensio-active ions. Thanks to PIV analysis, we identify four different flow stages. The transition between them can be understood by considering the competition between the Marangoni flow and the mass conservation flow, usually responsible for the coffee-ring pattern. We also demonstrate that the initial ionic concentration can select a coffee-ring pattern or a more homogeneous dried deposit.

Floating magnetic particles can self-assemble into structures. These structures are periodically deformed in a non reciprocal way using magnetic fields, which leads to controllable low Reynolds number locomotion.

The influence of relative humidity (RH) on the extremely slow compaction dynamics of a granular assembly has been experimentally investigated. Millimeter-sized glass beads are considered. Compaction curves are fitted by stretched exponentials with characteristic time τ and exponent δ, which are seen to be deeply affected by the moisture content. A kinetic model, taking into account both triboelectric and capillary effects, is in excellent agreement with our results. It confirms the existence of an optimal condition at a relative humidity ≈45% for minimizing cohesive interactions between glass beads. The exponent δ is seen to depend strongly on the diffusive character of grains and voids inside the packing: diffusion for cohesiveless particles and subdiffusion when cohesion plays a role. As a consequence, the RH represents a relevant parameter that should be reported for every experimental work on a slowly driven dense random packing.

Evaporation of sessile droplets is a way to organize suspended particles and create surface coating. Many studies have demonstrated that suspensions with various composition can give rise to qualitatively different dried patterns, often by focusing on the radial density pro le of deposited particles. We demonstrate that a single suspension of superparamagnetic colloids can give rise to several dried patterns thanks to an external magnetic eld applied during the evaporation process. We show the various patterns obtained with zero, constant, rotating and oscillating magnetic elds, and evidence the continuous control given by the intensity of a constant magnetic eld. We also show this magnetic control has a substantial e ect on the morphological details of the deposits.

The granular flow behavior of carbon nanotubes produced by the CCVD method in a laboratory continuous inclined rotary reactor and of a catalyst was experimentally studied using a rotating drum. The dynamic angle of repose of the bulk solid and the standard variation of the solid bed surface were determined as a function of rotational speed of the rotating drum and for several filling percentages of the drum. Whatever the carbon nanotube production conditions, the dynamic angle of repose and the standard variation of the solid bed depended only on the filling percentage of the drum. Results were very interesting for practical application to carbon nanotube production in an industrial continuous inclined rotary reactor, because the granular flow behavior was the same during the reaction throughout the length of the reactor and depended only on the reactor filling. A bed behavior diagram based on the drum rotational speed and on the drum filling percentage was also constructed experimentally. The flow behavior of the solid during carbon nanotube production was on the boundary between the slumping and the rolling modes, leading to a good mixing of gas and solid during the reaction and to an improvement of the mass and heat transfer in the bed. (c) 2008 Elsevier B.V. All rights reserved.

Particle engineering technologies have led to the commercialization of new inhaled powders like PulmoSolTM or PulmoSphereTM. Such platforms are produced by spray drying, a well-known process popular for its versatility, thanks to wide-ranging working parameters. Whereas these powders contain a high drug-loading, we have studied a low-dose case, in optimizing the production of powders with two anti-asthmatic drugs, budesonide and formoterol. Using a Design of Experiments approach, 27 powders were produced, with varying excipient mixes (cyclodextrins, raffinose and maltodextrins), solution concentrations, and spray drying parameters in order to maximize deep lung deposition, measured through fine particle fraction (next generation impactor). Based on statistical analysis, two powders made of hydropropyl-β-cyclodextrin alone or mixed with raffinose and L-leucine were selected. Indeed, the two powders demonstrated very high fine particle fraction (>55%), considerably better than commercially available products. Deep lung deposition has been correlated to very fine particle size and lower microparticles interactions shown by laser diffraction assays at different working pressures, and particle morphometry. Moreover, the two drugs would be predicted to deposit homogeneously into the lung according to impaction studies. Uniform delivery is fundamental to control symptoms of asthma. In this study, we develop carrier-free inhalation powders promoting very efficient lung deposition and demonstrate the high impact of inter-particular interactions intensity on their aerosolization behavior.

We present an original experimental study of the compaction dynamics for two-dimensional granular systems. Compaction dynamics is measured at three different scales: the macroscopic scale through the normalized packing fraction rho, the mesoscopic scale through the normalized fraction phi of hexagonal domains in the system, and the microscopic scale through the grain mobility mu. Moreover, the hexagonal domains are found to obey a growth process dominated by the displacement of domain boundaries. A global picture of compaction dynamics relevant at each scale is proposed.

Granular gravity driven flows of glass beads have been observed in a silo with a flat bottom. A dc high electric field has been applied perpendicularly to the silo to tune the cohesion. The outlet mass flow has been measured. An image subtraction technique has been applied to visualize the flow geometry and a spatiotemporal analysis of the flow dynamics has been performed. The outlet mass flow is independent of voltage, but a transition from funnel flow to rathole flow is observed. This transition is of probabilistic nature and an intermediate situation exists between the funnel and the rathole situations. At a given voltage, two kinds of flow dynamics can occur: a continuous flow or an intermittent flow. The electric field increases the probability to observe an intermittent flow.

We present an experimental study of the compaction dynamics for two-dimensional anisotropic granular systems. The compaction dynamics of rods is measured at three different scales: (i) the macroscopic scale through the packing fraction rho, (ii) the mesoscopic scale through both fractions of aligned grains phi(a) and ideally ordered grains phi(io), and (iii) the microscopic scale through both rotational and translational grain mobilities mu(r,t). At the macroscopic scale, we have observed two stages during the compaction process, suggesting different characteristic time scales for grain relaxation. At the mesoscopic scale, we have observed the formation and the growth of domains made of aligned grains during the first stage of compaction. At the late stage, these domains of aligned grains are sheared to form ideally ordered domains. From a microscopic point of view, measurements reveal that the beginning of the compaction process is essentially related to translational motions of the grains. The grain rotations drive mainly the process during the late stages of compaction.

Medicinal diagnosis requires the development of innovative devices allowing the detection of small amounts of biological species. Among the large variety of available biosensors, the ones based on fluorescence phenomenon are really promising. Here, we show a prototype of the basic unit of a multi-sensing biosensor combining optics and microfluidics benefits. This unit makes use of two crossed optical fibers: the first fiber is used to carry small probe molecules droplets and excite fluorescence, while the second one is devoted to target molecules droplets transport and fluorescence detection. Within this scheme, the interaction takes place in each fiber node. The main benefits of this detection setup are the absence of fibers functionalization, the use of microliter volumes of target and probe species, their separation before interaction, and a better detection limit compared to cuvettes setups.

Recent works demonstrated that fiber arrays may constitute new means of designing open digital microfluidic systems. Various processes, such as droplet motion, fragmentation, trapping, release, mixing and encapsulation, may be achieved on fiber arrays. However, handling a large number of tiny droplets resulting from the mixing of several liquid components is required for developing microreactors, smart sensors or microemulsifying drugs. Here, we show that the manipulation of tiny droplets onto fiber networks allows for creating compound droplets with a high complexity level. Moreover, this cost-effective and adjustable method may also be implemented with optical fibers in order to develop fluorescence-based biosensor.

Droplets on fibers have been extensively studied in the recent years. Although the equilibrium shapes of simple droplets on fibers are well established, the situation becomes more complex for compound fluidic systems. Through experimental and numerical investigations, we show herein that compound droplets can be formed on fibers and that they adopt specific geometries. We focus on the various contact lines formed at the meeting of the different phases and we study their equilibrium state. It appears that, depending on the surface tensions, the triple contact lines can remain separate or merge together and form quadruple lines. The nature of the contact lines influences the behavior of the compound droplets on fibers. Indeed, both experimental and numerical results show that, during the detachment process, depending on whether the contact lines are triple or quadruple, the characteristic length is the inner droplet radius or the fiber radius.

The growing interest for Selective Laser Melting (SLM) in orthopedic implant manufacturing is accompanied by the introduction of novel Ti alloys, in particular β-Ti for their excellent corrosion resistance as well as favorable combination of high mechanical strength, fatigue resistance and relatively low elastic modulus. As part of the SLM process for producing quality β-Ti parts powder flowability is essential to achieve uniform thickness of powder layers. In this work the flowability of different gas atomized β-Ti, including NiTi, powders has been studied. Their rheological properties were compared to those of commercially available plasma-atomized Ti–6Al–4V powder using a newly developed semi-automatic experimental set-up. Not only the particle size, shape and size distribution of the powders display a large influence on the powder flowability but also particle surface properties such as roughness, chemical composition and the presence of liquid on the surface of the particles. It was found that plasma or gas atomization production techniques for SLM powder have a considerable effect on the particle topography. Among the powders studied regarding SLM applicability only rheological properties of the fine size fraction (25–45 μm) of Ti–45Nb didn't conform to SLM processing requirements. To improve flowability of the Ti–45Nb powder itwas annealed both in air and argon atmosphere at 600 °C during 1 h, resulting in an improved rheological behavior suitable for SLM processing.

When a droplet is placed onto a vertically vibrated bath, it can bounce without coalescing. Upon an increase of the forcing acceleration, the droplet is propelled by the wave it generates and becomes a walker with a well-defined speed. We investigate the confinement of a walker in different rectangular cavities, used as waveguides for the Faraday waves emitted by successive droplet bounces. By studying the walker velocities, we discover that one-dimensional confinement is optimal for narrow channels of width of D≃1.5λF. Thereby, the walker follows a quasilinear path. We also propose an analogy with waveguide models based on the observation of the Faraday instability within the channels.

CdSe nanoparticles are of great interest for many applications. However, their size, shape, and aggregation are still difficult to control by the conventional synthesis methods. Here, we report on the synthesis of CdSe quantum dots (QDs), with an average diameter less than 10 nm, using radio-frequency magnetron sputtering (RFMS) on glass and silicon substrates at 25 °C. First, results show that a target-substrate distance of 13.5 cm and a chamber pressure of 2.2 .10-1 mbar were required to deposit a CdSe QDs layer on the substrates. The morphology and optical properties of CdSe QDs were then studied as a function of RF power and deposition time. The size of CdSe QDs increases with increasing both the RF power and the deposition time. UV-visible spectroscopy shows that the CdSe QDs layer deposited on the glass-substrate by RFMS has almost the same optical properties as the one obtained from commercial CdSe QDs solutions. In both cases, a shift of the characteristic absorption band of CdSe QDs towards the higher wavenumbers is observed with the QDs size increase. AFM confirms the success of CdSe QDs layer deposition by RFMS: CdSe QDs with a mean diameter of 7.5 ± 2 nm were observed for a RF power of 14 W, a chamber pressure of 2.2 .10-1 mbar, a target-substrate distance of 13.5 cm and a deposition time of 7.5 min (optimal values). With these parameters, the coverage of the substrate by the nano-objects is estimated at 25-30 % of the overall surface.

Non-volatile resistive memory cells are promising candidates to tremendously impact the further development of Boolean and neuromorphic computing. In particular, nanoscale memory-bit cells based on electromigration (EM)-induced resistive switching in monolithic metallic structures have been identified as an appealing and competitive alternative to achieve ultrahigh density while keeping straightforward manufacturing processes. In this work, we investigate the EM-induced resistance switching in indented Al microstrips. In order to guarantee a large switching endurance, we limited the on-to-off ratio to a minimum readable value. Two switching protocols were tested, (i) a variable current pulse amplitude adjusted to ensure a precise change of resistance, and (ii) a fixed current pulse amplitude. Both approaches exhibit an initial training period where the mean value of the device’s resistance drifts in time, followed by a more stable behavior. Electron microscopy imaging of the devices show irreversible changes of the material properties from the early stages of the switching process. High and low resistance states show retention times of days and endurances of∼10^3 cycles.

Magnetic metamaterials have demonstrated promising perspectives to improve the efficiency of magnetic flux concentrators. In this work, we investigate the effects of downscaling these devices for on-chip integration. We scrutinize the influence of the non-linear magnetic response of the ferromagnetic components, their magnetic irreversibility, the formation of magnetic domains, as well as the effects of geometry and size of the devices. Our results demonstrate that the implementation of metasurfaces at the microscale opens up new technological possibilities for enhancing the performance of magnetic field detectors and remotely charging small electric devices, thus paving the way towards new approaches in information and communication technologies.

The influence of a conducting layer on the magnetic flux penetration in a superconducting Nb film is studied by magneto-optical imaging. The metallic layer partially covering the superconductor provides an additional velocity-dependent damping mechanism for the flux motion that helps protecting the superconducting state when thermomagnetic instabilities develop. If the flux advances with a velocity slower than w = 2/µ0σt, where σ is the cap layer conductivity and t is its thickness, the flux penetration remains unaffected, whereas for incoming flux moving faster than w, the metallic layer becomes an active screening shield. When the metallic layer is replaced by a perfect conductor, it is expected that the flux braking effect will occur for all flux velocities. We demonstrate this effect by investigating Nb samples with a thickness step. Some of the observed features, namely the deflection and the branching of the flux trajectories at the border of the thick centre, as well as the favoured flux penetration at the indentation, are reproduced by time-dependent Ginzburg-Landau simulations.

We investigate targeted and localized material modifications produced by electropulsing of Al-capped Nb microbridges with a multiterminal configuration. The affected regions of the Nb/Al bilayer terminals are revealed by an in-lens secondary-electron detector in a scanning electron microscope and by Kelvin-probe force microscopy, both suggesting a decrease in the work function in the modified areas. In contrast, the affected areas are neither apparent through an Everhart-Thornley secondary-electron detector nor through atomic force microscopy, which indicates little morphological change in the microstructure. In addition, we demonstrate that the extent of the electroannealed regions is strongly influenced by the terminal geometry. These results are captured by complementary finite-element modeling, which permits us to estimate that a threshold temperature of 435±35 K is needed to induce material modifications. These findings provide further insights into the subtle modifications produced by gentle electroannealing of Nb/Al microstructures and represent a step forward towards mastering this emerging nanofabrication technique.

Hypothesis Metallic nanowires, particularly polyol-grown silver nanowires, exhibit a morphological instability at temperatures significantly lower than their bulk melting point. This instability is commonly named after Rayleigh's description of the morphological instability of liquid jets, even though it has been shown that its quantitative predictions are not consistent with experimental measurements. In 1996, McCallum et al. proposed a description of the phenomenon assuming a solid wire lying on a substrate. It is assumed that the latter description depicts more accurately the reality. Experiments Nanowires with varying diameters have been deposited on silicon wafers. Statistical analysis of their radius and the wavelength of their periodical instability have been performed. Findings McCallum et al.'s model better aligns with experimental observations compared to Rayleigh's description. This validation provides a robust theoretical framework for enhancing the stability of nanowires, addressing a crucial aspect of their development.

Simultaneous optical microscopy and electric transport measurements on La0.7Sr0.3MnO3 nanobridges, grown on SrTiO3 (STO), show direct evidence of directional oxygen vacancy migration under large voltage bias. Comparative study on discontinuous structures, with voltages applied across a micron-scale gap, demonstrates that high electric fields induce electrolytic modifications confined to the anode. Extensive electromigration is shown to induce the formation of linear surface scars on the STO substrate, following well defined crystallographic directions. The reproducible triggering of these surface dislocations is demonstrated, unveiling their thermal rather than electrical origin and it is shown that they do not represent electroformed conduction channels. High-resolution scanning transmission electron microscopy imaging reveals that the scars correspond to nanometer scale steps caused by (101) gliding planes in the STO caused by the proliferation of edge dislocations and local lattice expansion. These findings shed light on selective electrically-controlled atom migration and its role in structural modification of functional oxides, opening a unique avenue for ionotronic device design.

Sudden avalanches of magnetic flux bursting into a superconducting sample undergo deflections of their trajectories when encountering a conductive layer deposited on top of the superconductor. Remarkably, in some cases the flux is totally excluded from the area covered by the conductive layer. We present a simple classical model that accounts for this behaviour and considers a magnetic monopole approaching a semi-infinite conductive plane. This model suggests that magnetic braking is an important mechanism responsible for avalanche deflection.

Local polarization of a magnetic layer, a well-known method for storing information, has found its place in numerous applications such as the popular magnetic drawing board toy or the widespread credit cards and computer hard drives. Here we experimentally show that a similar principle can be applied for imprinting the trajectory of quantum units of flux (vortices), travelling in a superconducting film (Nb), into a soft magnetic layer of permalloy (Py). In full analogy with the magnetic drawing board, vortices act as tiny magnetic scribers leaving a wake of polarized magnetic media in the Py board. The mutual interaction between superconducting vortices and ferromagnetic domains has been investigated by the magneto-optical imaging technique. For thick Py layers, the stripe magnetic domain pattern guides both the smooth magnetic flux penetration as well as the abrupt vortex avalanches in the Nb film. It is however in thin Py layers without stripe domains where superconducting vortices leave the clearest imprints of locally polarized magnetic moment along their paths. In all cases, we observe that the flux is delayed at the border of the magnetic layer. Our findings open the quest for optimizing magnetic recording of superconducting vortex trajectories.

Efficient conversion of a spin signal into an electric voltage in mainstream semiconductors is one of the grand challenges of spintronics. This process is commonly achieved via a ferromagnetic tunnel barrier, where nonlinear electric transport occurs. In this work, we demonstrate that nonlinearity may lead to a spin-to-charge conversion efficiency larger than 10 times the spin polarization of the tunnel barrier when the latter is under a bias of a few millivolts. We identify the underlying mechanisms responsible for this remarkably efficient spin detection as the tunnel-barrier deformation and the conduction-band shift resulting from a change of applied voltage. In addition, we derive an approximate analytical expression for the detector spin sensitivity P_det(V). Calculations performed for different barrier shapes show that this enhancement is present in oxide barriers as well as in Schottky-tunnel barriers, even if the dominant mechanisms differ with the barrier type. Moreover, although the spin signal is reduced at high temperatures, it remains superior to the value predicted by the linear model. Our findings shed light onto the interpretation and understanding of electrical spin-detection experiments and open paths to optimizing the performance of spin-transport devices.

Abstract Topology is a crucial ingredient for understanding the physical properties of superconductors. Magnetic field crowds to adopt the form of topologically-protected quantum flux lines which can lose this property when moving at high velocities. These extreme conditions can be realized when superconductors undergo a thermomagnetic instability for which the sample topology come also into play. In this work, utilizing the magneto-optical imaging technique, we experimentally study magnetic flux avalanches in superconducting films with multiply-connected geometries, including single and double rings. We observe a domino effect in which avalanches triggered at the outer ring, stimulate avalanches at the inner ring thus impairing the expected magnetic shielding resulting from the outer ring and gap. We implement numerical simulations in order to gain more insight into the underlying physical mechanism and demonstrate that such event is not caused by the heat conduction, but mainly attributed to the local current distribution variation near the preceding flux avalanche in the outer ring, which in turn has a ripple effect on the local magnetic field profile in the gap. Furthermore, we find that the domino effect of thermomagnetic instabilities can be switched on/off by the environmental temperature and the gap width between the concentric rings. These findings provide new insights on the thermomagnetic instability in superconducting devices with complex topological structures, such as the superconductor–insulator–superconductor multilayer structures of superconducting radio-frequency cavities.

Graphene is a promising substrate for future spintronic devices owing to its remarkable electronic mobility and low spin-orbit coupling. Hanle precession in spin-valve devices is commonly used to evaluate spin diffusion and spin lifetime. In this work, we demonstrate that this method is no longer accurate when the distance between the inner and outer electrodes is smaller than 6 times the spin diffusion length, leading to errors as large as 50% for the calculation of the spin figures of merit of graphene-based devices. We suggest simple but efficient approaches to circumvent this limitation by addressing a revised version of the Hanle fit function. Complementarily, we provide clear guidelines for the design of four-terminal nonlocal spin valves suitable for the flawless determination of the spin lifetime and the spin diffusion coefficient.

We present a thorough investigation by magneto-optical imaging of the magnetic flux penetration in Nb thin films with lithographically defined border indentations. We demonstrate that discontinuity lines (d-lines), caused by the abrupt bending of current streamlines around the indentations, depart from the expected parabolic trend close to the defect and depend on the shape and size of the indentation as well as on the temperature. These findings are backed up and compared with theoretical results obtained by numerical simulations and analytical calculations highlighting the key role played by demagnetization effects and the creep exponent n. In addition, we show that the presence of nearby indentations and submicrometer random roughness of the sample border can severely modify the flux front topology and dynamics. Strikingly, in contrast to what has been repeatedly predicted in the literature, we do not observe that indentations act as nucleation spots for flux avalanches, but they instead help to release the flux pressure and avoid thermomagnetic instabilities.

Electron spin resonance spectroscopy (ESR) of the nitroxide labelled fatty acid probes (5-, 16-doxyl stearic acid) was used to monitor the micelle microviscosity of three surfactants at various concentrations in aqueous solution: sodium dodecyl sulphate (SDS), dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB). At low surfactant concentration, there is no micelle, the ESR probe is dissolved in water/surfactant homogeneous phase and gives his microviscosity. At higher surfactant concentration, an abrupt increase in microviscosity indicates the apparition of micelles and, the solubilization of the probes in micelles. The microviscosity of the three surfactants, in a large surfactant range, was obtained as well as the critical micelle concentration (CMC). The microviscosity increased slightly with the increase in surfactant concentration. Phosphate buffer lowered the CMC value and generally increased the microviscosity. (c) 2006 Elsevier B.V. All rights reserved.

The functionalization of aliphatic polyesters by the copper-mediated azide–alkyne Huisgen’s cycloaddition is very efficient under mild conditions, which prevents degradation from occurring. The implementation of this reaction requires the synthesis of aliphatic polyesters bearing pendant alkynes and azides, which can be carried out either by polycondensation or by ring-opening polymerization.

The synthesis of aliphatic polyesters by the ring-opening polymerization of cyclic monoesters was discovered by Carothers in the 1930s. Since then, a plethora of catalysts and initiators have been discovered to promote this polymerization. Nowadays, steadily increasing attention is paid to organocatalysts and, among them, acids, bases, and H-bond donors and acceptors. Organocatalysts today available for the polymerization of medium size cyclic monoesters such as δ-valerolactone and ε-caprolactone will be reviewed. Special attention will be paid to dual catalysts capable of activating both the initiator and the monomer. The most efficient catalysts promote fast and selective ring-opening polymerization. The mechanism based either on ionic interactions, the establishment of H-bonds or nucleophilic activation will be discussed. The importance of ring size will be highlighted by the organocatalyzed polymerization of β-butyrolactone, γ-butyrolactone and pentadecalactone as a typical macrocyclic monoester.

Polylactones are important biodegradable and biocompatible environmentally friendly polyesters widely used for many applications and more particularly for biomedical applications. This review covers recent advances dealing with their synthesis by ring-opening polymerization (ROP). First, lactones polymerized by ROP will be reviewed with special attention paid to the effect of the ring size on polymerizability. Aliphatic polyesters synthesized by the ROP of lactones can also be obtained by polycondensation. The advantages of ROP compared with polycondensation will be highlighted. The second section is devoted to the different mechanisms used to carry out ROP, such as anionic, coordination, cationic, enzymatic, and organocatalytic polymerization. Special attention will be paid to the control imparted to the polymerization by the use of catalysts and initiators. The polymerization of lactones substituted by functional groups will be shown to afford functionalized aliphatic polyesters. The final section will focus on the synthesis of different architectures such as star-shaped, graft, hyperbranched, and macrocyclic polylactones in the frame of macromolecular engineering.

Two main strategies aiming at synthesizing aliphatic polyesters bearing pendant functional groups will be reported. The first one is based on the synthesis and the polymerization of lactones substituted by various functional groups. The direct grafting of functional groups onto aliphatic polyesters is the second strategy. Last but not least, the association of these two strategies is very promising in order to overcome their respective limitations.

Low viscosity (< 100 cSt) silicon oil droplets are placed on a high viscosity (1000 cSt) oil bath that vibrates vertically. The viscosity difference ensures that the droplet is more deformed than the bath interface. Droplets bounce periodically on the bath when the acceleration of its sinusoidal motion is larger than a threshold value. The threshold is minimum for a particular frequency of excitation: droplet and bath motions are in resonance. The bouncing droplet has been modeled by considering the deformation of the droplet and the lubrication force exerted by the air layer between the droplet and the bath. Threshold values are predicted and found to be in good agreement with our measurements.

We report numerical investigations for the compaction dynamics of dense granular assemblies. The studies are based on the non-smooth contact dynamics model. Our work suggests that the dimensionless acceleration parameter Gamma, used by a large majortiy of authors, is not appropriate for rescaling the data. We prove that the dimensionless energy Xi, injected in the granular system at lift-off, is more appropriate and leads to robust interpretations of the compaction dynamics. Indeed, the injected energy allows to pass energy barriers that separate local equilibrium states. Using the Eyring picture of relaxation dynamic, we show that the consideration of Xi leads to a new law for compaction.

ABSTRACT : Droplets spontaneously move when they are placed at the tip of a cone surface. Using three dimensionally printed structures, we experimentally explore a large panel of configurations regarding the aperture angle of the cone. We evidence a change of the droplet geometry while moving along the conical fiber. This transition is a switch of configuration from barrel to clamshell shape. The consequence is a change in the droplet dynamics. We estimate the position of this geometrical transition and we propose two models to describe the motion of the barrel and the clamshell droplets. While both shapes are driven by capillary forces, the dissipation is dependent on the geometrical configuration. For barrel shape droplets the main dissipation appears to be in the liquid wedge. For clamshell shape droplets the dissipation occurs mainly in the liquid film close to the conical fiber.

Compaction dynamics and granular arches have been studied using the electrical resistance of a packing. An exponential decay of the resistance is found whatever the electrical current is. A fluctuation regime is then encountered. A characteristic relaxation time has been pointed out and is linked to the arch formation in the system. (C) 2002 Elsevier Science B.V. All rights reserved.

Various packings made of metallic grains have been electrically characterized. Electrical breakdown is observed in I-V curves. A well defined critical point separates the insulating and the conducting regime of the packing. The breakdown is reversible by submitting the packing to a small tap. This unusual property leads to hysteretic loops in I-V diagrams. The study of the behavior of I-V curves allows us to describe the system as a network of weak lossy contacts. The key parameter is the inner electrical field controlling the diode-like or diffusion-like state of the packing. (C) 2002 American Institute of Physics.

When an oil droplet is placed on a quiescent oil bath, it eventually collapses into the bath due to gravity. The resulting coalescence may be eliminated when the bath is vertically vibrated. The droplet bounces periodically on the bath, and the air layer between the droplet and the bath is replenished at each bounce. This sustained bouncing motion is achieved when the forcing acceleration is higher than a threshold value. When the droplet has a sufficiently low viscosity, it significantly deforms: spherical harmonic Y-1(m) modes are excited, resulting in resonant effects on the threshold acceleration curve. Indeed, a lower acceleration is needed when I modes with m = 0 are excited. Modes m not equal 0 are found to decrease the bouncing ability of the droplet. A break of degeneracy is observed for the m parameter. In particular, when the mode 1 = 2 and m = 1 is excited, the droplet rolls on the vibrated surface without touching it, leading to a new self-propulsion mode.

We show that a double emulsion (oil in water in oil) can be created starting from a compound droplet (surfactant solution in oil). The compound drop bounces on a vertically vibrated liquid surface. When the amplitude of the vibration exceeds a threshold value, the oil layer penetrates the water content and leaves a tiny oil droplet within. As this phenomenon occurs at each vigorous impact, the compound drop progressively transforms into a double emulsion. The emulsification threshold, which is observed to depend on the forcing frequency but not on the drop size, is rationalized by investigating the impact of compound drops onto a static liquid surface. The droplet creation occurs when the kinetic energy released at impact is larger than the energy required to deform the compound drop, namely when the Weber number is higher than a given threshold value.

The electrical resistance decay of a metallic granular packing has been measured as a function of time. This measurement gives information about the size of the conducting cluster formed by the well connected grains. Several regimes have been encountered. Chronologically, the first one concerns the growth of the conducting cluster and is identified to belong to diffusion processes through a stretched exponential behavior. The relaxation time is found to be simply related to the initial injected power. This regime is followed by a reorganization process due to thermal dilatation. For the long-term behavior of the decay, an aging process occurs and enhances the electrical contacts between grains through microsoldering. (C) 2003 American Institute of Physics.

Antibubbles are unusual fluid objects consisting of a thin spherical air shell surrounding a liquid globule. Here we study and analyze the aging of these inverted bubbles. The lifetime is found to be distributed along an exponential law. Moreover, the breakdown of the air film is observed to be the analogue of dewetting by spinodal decomposition. We interpret the long lifetime of the antibubbles as resulting from the slow drainage of the air until the film reaches a critical thickness. Then, van der Waals forces act, leading to the collapse of the film.

The partial coalescence of a droplet onto a planar liquid-liquid interface is investigated experimentally by tuning the viscosities of both liquids. The problem mainly depends on four dimensionless parameters: The Bond number (gravity vs surface tension), the Ohnesorge numbers (viscosity in both fluids vs surface tension), and the density relative difference. The ratio between the daughter droplet size and the mother droplet size is investigated as a function of these dimensionless numbers. Global quantities such as the available surface energy of the droplet have been measured during the coalescence. The capillary waves propagation and damping are studied in detail. The relation between these waves and the partial coalescence is discussed. Additional viscous mechanisms are proposed in order to explain the asymmetric role played by both viscosities.

When a low viscosity oil droplet is laid onto the surface ofa high viscosity oil liquid, it stays at rest for a moment before coalescence. The coalescence can be delayed and sometimes inlibited by injecting fresh air under the droplet. This can happen when the surface ofthe bath oscillates vertically. In this case the droplet basically bounces on the interface. We obsewe that the conditions for bouncing depends on the frequency, more precisely we observe resonance when the eigenfrequency of the droplet is excited. In some conditions, a droplet presents a non axi- symmetric mode of deformation. That leads to a rotation of the droplet and to a horizontal displacement.

The electrical resistance of a metallic granular packing has been recorded at room temperature. A nearby burster between which sparks are produced, induces a decrease in the resistance of the granular packing as described in the works of Branly. Our measurements emphasize that the decrease is continuous and the resistance variations behave like a stretched exponential law due to the creation of new electrical paths as in nucleation-growth soldering processes. This behavior has been identified to be a diffusionlike process.

We propose a lattice model for studying the compaction of granular mixtures under taps. Two granular species are considered: small grains with low mobilities and T-shaped grains characterized by a larger ability to move. When those grains are mixed together, the compaction dynamics is mainly controlled by the volume fraction x of the small grains. Segregation have been found on the top layers of the pile. The grain mobilities have been studied for different values of the volume fraction x. An effective grain mobility has been defined for the mixture. This mobility is given by the linear combination of the mobility of both pure species minus a non-linear interaction term. Finally, the compaction speed depends on the fraction of the anisotropic grains.

The electrical properties of a 2D packed metallic pentagons have been studied. The electrical characterization of such metallic pentagon heaps, like i - V measurements, has been achieved. Two distinct regimes have been shown. They are separated by a transition line along which the system exhibits a memory effect behavior due to the irreversible improvement of electrical contacts between pentagons (hot spots). A limit current density has been found.

When a droplet is gently laid onto the surface of the same liquid, it stays at rest for a moment before coalescence. The coalescence can be delayed and sometimes inhibited by injecting fresh air under the droplet. This can happen when the surface of the bath oscillates vertically. In this case the droplet basically bounces on the interface. The lifetime of the droplet has been studied with respect to the amplitude and the frequency of the excitation. The lifetime decreases when the acceleration increases. The thickness of the air film between the droplet and the bath has been investigated using interference fringes obtained when the system is illuminated by low-pressure sodium lamps. Moreover, both the shape evolution and the motion of the droplet center of mass have been recorded in order to evidence the phase offset between the deformation and the trajectory. A short lifetime is correlated to a small air-film thickness and to a large phase offset between the maximum of deformation and the minimum of the vertical position of the center of mass.

A method is proposed to stop the cascade of partial coalescences of a droplet laid on a liquid bath. The strategy consists of vibrating the bath in the vertical direction in order to keep small droplets bouncing. Since large droplets are not able to bounce, they partially coalesce until they reach a critical size. The system behaves as a low pass filter: droplets smaller than the critical size are selected. This size has been investigated as a function of the acceleration and the frequency of the bath vibration. Results suggest that the limit size for bouncing is related to the first mode of the droplet deformation.

A toy model of granular compaction which includes some resistance due to granular arches is proposed. In this model, the solid/solid friction of contacting grains is a key parameter and a slipping threshold omega(c) is defined. Realistic compaction behaviors have been obtained. Two regimes separated by a critical point omega(c)* of the slipping threshold have been emphasized: (i) a slow compaction with lots of paralyzed regions and (ii) an inverse logarithmic dynamics with a power-law scaling of grain mobility. Below the critical point omega(c)*, the physical properties of this frozen system become independent of omega(c). Above the critical point omega(c)*-i.e., for low friction values-the packing properties behave as described by the classical Janssen theory for silos.

A DC electrical current is injected through a chain of metallic beads. The electrical resistance of each bead- bead contacts is measured. At low current, the distribution of these resistances is large and log- normal. At high enough current, the resistance distribution becomes sharp and Gaussian due to the creation of microweldings between some beads. The action of nearby electromagnetic waves ( sparks) on the electrical conductivity of the chain is also studied. The spark effect is to lower the resistance values of the more resistive contacts, the best conductive ones remaining unaffected by the spark production. The spark is able to induce through the chain a current enough to create microweldings between some beads. This explains why the electrical resistance of a granular medium is so sensitive to the electromagnetic waves produced in its vicinity.

A compound drop is made of a millimetric water drop encapsulated in an oil shell. They are obtained by merging one drop of each component (water and oil). Afterwards, they are laid on a high viscosity oil bath which is vertically vibrated. When the forcing acceleration is higher than a given threshold Γth, compound drops can bounce on the surface. We show that above a second threshold Γe > Γth some oil contained in the shell enters in the inner water droplet forming a stable double emulsion.

The electrical properties of a two-dimensional packing of metallic beads are studied. Small mechanical perturbations of the packing lead to giant voltage fluctuations. Fluctuations are found to be non-Gaussian and seem to belong to Levy stable distributions. Anticorrelations have been also found for the sign of these fluctuations.

The effects of oxygen partial pressure during thermal treatment on the color and microstructure of Bizen, a traditional Japanese stoneware, were studied through model experiments using clay pellets covered lightly with rice straw as a coloring assistant. When heated in flowing nitrogen, the model pellet turned blackish owing to the formation of alpha-Fe particles coated with graphite. However, schreibersite (Fe3P), which is also blackish, was formed specifically on the pellet surface in direct contact with the straw. The rice straw seems to have generated a strongly reducing atmosphere, strong enough for the metallization to alpha-Fe, and also to have provided phosphorus through contact. When oxygen content in the surrounding gas atmosphere was raised to N-2/O-2=99/1, the pellet surface turned yellowish brown because the main coloring material was Fe3+-containing mullite. At oxygen contents of N-2/O-2=98/2 or more, the formation of hematite (alpha-Fe2O3) pushed the color to deep red.

Lead-free Cs2AgBiBr6 double perovskite is considered a promising alternative photovoltaic absorber to the widely used lead halide perovskite due to its easy processability, high stability, and reduced toxicity. Herein, for the first time spray processing for the deposition of Cs2AgBiBr6 double perovskite thin films is reported. Microstructural (X-ray diffraction, scanning electron microscopy) and optoelectronic (absorbance, photoluminescence, photocurrent density versus applied voltage curves, electrochemical impedance spectroscopy) properties of spray-coated film are compared with the spin-coated benchmark. Incorporation of the spray-coated Cs2AgBiBr6 double perovskite thin films in solar cells leads to a 2.3% photoconversion efficiency with high open-circuit voltage of 1.09 V. This study highlights the suitability of ultrasonic spray deposition for the optimization of Cs2AgBiBr6 solar cells in terms of light absorption properties and charge transfer at the Cs2AgBiBr6/hole transporting layer interface.

Concurrently to research conducted on ordinary Portland cement (PC), new types of binders were developed during the last decades. These are formed by alkali-activation of metakaolin or ground-granulated blast furnace slag (GGBFS) and are named, respectively, geopolymers (GP) or alkali-activated slag (AAS). Four different cementitious materials were synthesised: PC, AAS, GP, and a mix GP-AAS and fully compared about their compositions and (micro)-structures. X-ray diffraction has revealed the presence of semi-crystalline C-S-H gel binding phase in PC while AAS, GP and GP-AAS are nearly amorphous. Progressive structural changes have been observed between the different samples by means of infrared spectroscopy, Si-29 and At-27 magic-angle-spinning nuclear magnetic resonance spectroscopy: there is a polymerisation extent of the (alumino)-silicate framework from PC [SiQ(1) and SiQ(2) units] to AAS [SiQ(2) and SiQ(2)(1Al) units] and finally to GP [SiQ(4)(2Al) and SiQ(4)(3Al) units]. Scanning electron microscopy has shown that GP is a homogeneous matrix while the other materials are composites containing GGBFS grains surrounded by a binding matrix. Energy dispersive X-ray EDX analyses (line scans) have shown the absence of formation of any specific phase at the matrix-grains interfaces. (c) 2006 Elsevier Ltd. All rights reserved.

The additional energy spread due to sample porosity was implemented in the SIMNRA simulation code, version 6.60 and higher. Deviations of the path length and energy loss distributions from the ones expected from a Poisson distribution of the number of traversed pores are taken into account. These deviations are due to the interaction of pores at higher pore concentrations by overlap or blocking. The skewnesses of the energy distributions are approximated by two-piece normal distributions with identical first three moments. Propagation of porosity-induced energy spread in thick layers is taken into account. Calculated results are compared to experimental data obtained with thin TiO2 mesoporous films measured by Rutherford backscattering (RBS),transmission electron microscopy (TEM), and atmospheric poroellipsometry.

Cs2AgBiBr6 double perovskite compounds have been increasingly studied in recent years as promising candidates able to counter polluting, harmful and oxygen/moisture sensitive issues intrinsic to traditional lead-containing solar cells. Exhibiting high optical absorption coefficient, low toxicity and important structural stability, Cs2AgBiBr6 solar cells still suffer from limited absorption of low energy photons, low carrier mobility, and limited carrier lifetimes induced by defect states. Herein, for the first time, a molecular layer of tetracene has been introduced within a Cs2AgBiBr6-based photovoltaic architecture: being incorporated at the interface between the double perovskite photoabsorber and Spiro-OMeTAD hole transport material, tetracene allows for a suitably graded cascade of energy bands within the solar cell architecture, which ultimately improves interfacial charge transfers and reduces charge recombinations. The performances in photovoltaic devices are consequently enhanced vs. tetracene-free configurations, with champion values of open circuit voltages of 1.1 V (vs. 1.0 V), current densities of 2.5 mA/cm² (vs. 1.9 mA/cm²) and photoconversion efficiencies of 1.7% (vs. 1.3%) with reduced hysteretic behavior.

Mesostructured silica phases with lamellar structure were prepared by the liquid crystal templating (LCT) technique, from double chain alkylammonium surfactant and sodium silicate or tetraethylorthosilicate (TEOS) silica precursors. The structural characterization of these phases is presented and compared. Surface modification of the silica layers, together with elimination of the organic template, is considered. Finally, a representative model of the microstructural organization is proposed. (c) 2006 Elsevier Ltd. All rights reserved.

Silver paint has been tested as a soldering agent for DyBaCuO 4 single-domain welding. Junctions have been manufactured on Dy-Ba-Cu-O single domains cut either along planes parallel to the c-axis IT or along the ab-planes. Microstructural and superconducting characterizations of the samples have been performed. For both types of junctions, the microstructure in the joined area is very clean: no secondary phase or Ag particle segregation has been observed. Electrical and magnetic measurements for all configurations of interest are reported (rho(T) curves, and Hall probe mapping). The narrow resistive superconducting transition reported for all configurations shows that the artificial junction does not affect significantly the measured superconducting properties of the material.

A copper hydroxynitrate of stoichiometry Cu-2(OH)(3)NO3, analogous to the layered double hydroxide family, was synthesized by the so-called controlled double jet precipitation technique, and by hydrolysis of urea in the presence of copper nitrate. Special attention has been focused on the size, morphology and agglomeration tendency of the particles. The aim of this work is to define the optimum precipitation conditions in terms of quality and dispersability of the recovered product. Such platelet-like particles Can be used as anisotropic fillers in nanocomposite materials. Several reaction parameters such as flow and concentration of the reactant solutions, design of the reactor and addition of a growth modifier were studied. (C) 2003 Elsevier -Science B.V. All rights reserved.

Light management strategies using photonic crystals have been proven to efficiently improve light harvesting and subsequently conversion efficiency of various optoelectronic devices. This study focuses on 3D inverse opal CH3NH3PbI3 photoanodes in perovskite solar cells from a combined numerical and experimental approach. Varying the pore size and the layer thickness in numerical simulations, we first determined theoretical optimum from a purely optical point of view. Corresponding 3D inverse opal photonic nanostructures were then fabricated through spin-coating protocols using polystyrene nanospheres of various diameters as hard templating sacrificial agents. It demonstrates how the photonic nanostructuration of the perovskite layer impacts both optical and electronic properties of experimental samples. Regarding the individual 3D inverse opal perovskite layers, an optimum of light absorption is reached for an ∼500 nm diameter pore photonic nanostructure, with a photonic absorption enhancement as high as 16.1% compared to an unstructured compact benchmark. However, in addition to electronic-related countereffects, local light absorption in the hole transporting material is observed in assembled solar cells, weakening the light management benefits of the perovskite layer nanostructuration to only ∼3% photonic enhancement.

This work describes an electron backscattered diffraction (EBSD) study of the perovskite-derived structures YBa2Cu3O7-delta. After having pointed out the difficulties of EBSD analyses in resolving the orientations of these pseudo-cubic structures, various YBaCuO bulk samples are analysed and the correlation between the microstructure, crystal growth and global texture, determined by neutron diffraction, is carried out. Homogeneous 'microtexture' with small subdomain misorientation of 12 degrees are measured for YBCO top seeding melt textured growth (TSMTG) samples. YBCO perforated samples also exhibit misoriented subdomains, giving rise to a heterogeneous 'microtexture' correlated to the YBCO growth front and to the pattern used for the perforating.

The never-ending race towards miniaturization of devices induced an intense research in the manufacturing processes of the components of those devices. However, the complexity of the process combined with high equipment costs makes the conventional lithographic techniques unfavorable for many researchers. Through years, nanosphere lithography (NSL) attracted growing interest due to its compatibility with wafer-scale processes as well as its potential to manufacture a wide variety of homogeneous one-, two-, or three-dimensional nanostructures. This method combines the advantages of both top-down and bottom-up approaches and is based on a two-step process: (1) the preparation of a colloidal crystal mask (CCM) made of nanospheres and (2) the deposition of the desired material through the mask. The mask is then removed and the layer keeps the ordered patterning of the mask interstices. Many groups have been working to improve the quality of the CCMs. Throughout this review, we compare the major deposition techniques to manufacture the CCMs (focusing on 2D polystyrene nanospheres lattices), with respect to their advantages and drawbacks. In traditional NSL, the pattern is usually limited to triangular structures. However, new strategies have been developed to build up more complex architectures and will also be discussed.

Among other applications, magnesium hydroxide is commonly used as a flame-retardant filler in composite materials, as well as a precursor for magnesium oxide refractory ceramic. The microstructure of the powder is of prime importance in both technical applications. The influence of synthesis parameters on the morphological characteristics of magnesium hydroxide nanoparticles precipitated in dilute aqueous medium was studied. Several parameters were envisaged such as chemical nature of the base precipitant, type of counter-ion, temperature and hydrothermal treatment. Special attention was given to the obtaining of platelet-shaped, nanometric and de-agglomerated powders. The powders were characterized in terms of particle size distribution, crystal habits, morphology and ability to be redispersed in water. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and laser diffusion analyses were used for this purpose. (C) 2002 Elsevier Science B.V. All rights reserved.

A lamellar mesostructured silica was subjected to a progressive heat treatment in order to study its structural evolution and the characteristics of the resulting calcined powder. By combining informations from several physical methods, i.e. TG-DTA, XRD, TEM and nitrogen adsorption, it has been possible to evidence the formation of very small particles of silica at a temperature around 450 degreesC, exhibiting a very high value of aspect ratio, consequently to the template loss by combustion. By increasing the temperature above 530 degreesC, the dehydroxylation promotes a decrease in the surface area, followed by the sintering process at higher temperature, which nearly annihilate the surface area of the particles. (C) 2003 Elsevier Science Ltd. All rights reserved.

The intercalation and de-intercalation of lithium cations in electrochromic tungsten oxide thin films are significantly influenced by their structural and surface characteristics. In this study, we prepared two types of amorphous films via the sol-gel technique: one dense and one mesoporous in order to compare their response upon lithium intercalation and de-intercalation. According to chronoamperometric measurements, Li+ intercalates/de-intercalates faster in the mesoporous film (24s/6s) than in the dense film (48s/10s). The electrochemical measurements (cyclic voltammetry and chronoamperometry) also showed worse reversibility for the dense film compared to the mesoporous film, giving rise to important Li+ trapping and remaining coloration of the film. Raman analysis showed that the mesoporous film provides more accessible and various W-O surface bonds for Li+ intercalation. On the contrary, in the first electrochemical insertion and de-insertion in the dense film, Li+ selectively reacts with a few surface W-O bonds and preferentially intercalates into pre-existing crystallites to form stable irreversible LixWO3 bronze.

In this article, we propose a new solar concentrator based on spectral splitting of sunlight. Spectral splitting has the objective to collect different spectra onto spectrally adapted solar cells for a more efficient use of the Sun’s spectrum. Its combination with solar concentration makes an alternative to classical technologies. The proposed concentrator is composed of a diffractive/refractive optical element that spectrally splits and focuses the light onto a waveguide. The light is then conducted by total internal reflection towards the two specific solar cells. The optical concept and optimization of each element is presented in this paper. An adaptation for dye sensitized solar cells is performed. A geometrical factor around 5× is reached. Finally, theoretical optical efficiency, the manufacturing process and experimental testing with a collimated Sun simulator are presented.

Anatase mesoporous TiO2 thin films are frequently prepared by surfactant templating to control porosity development and Atmospheric Ellipsometric Porosimetry is a reliable and fast technique allowing the determination of the porosity of such films. After prolonged exposition to high-vacuum (6×10-6 mbar), the films porosity exhibits a degraded behavior during porosimetric measurements, indicating a vacuum-induced modification. The main effect resulting from such exposition to high-vacuum is a wet- tability modification of the films, resulting in an increase of the hydrophobic character of the TiO2 surface. This evolution induces non-correct results in porosimetric measurements due to the fact that the contact angle parameter needed to calculate the pore size distribution is highly different from the reference films. A surface contamination explains such modifications and a restoration of the films is obtained by using ultraviolet treatment.

Mesoporous anatase thin films were prepared by the evaporation-induced self-assembly process. This paper reports a study of the influence of several physical parameters on the long-range ordering of the mesopores. A preliminary study was done to set the best humidity conditions during dip-coating and ageing of the films. The withdrawal speed, already known to modify the thickness of the deposited film, was shown to exert a strong influence on the percentage of porosity. This was studied by step profilometry combined with Rutherford backscattered spectrometry (RBS). In parallel, small angle X-ray scattering (SAXS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and RBS were used to tune the precise thermal treatment applied to the so-obtained films, in order to preserve the porous mesostructure and promote the nanocrystallization of anatase TiO2.

The biomineralization of otoliths results mainly from the release of soluble Ca(2+), which is in turn precipitated as CaCO(3) crystals. In some Carapidae, sagittae sections have been shown to reveal a three-dimensional asymmetry with a nucleus close to the sulcal side, an unusual position. This study seeks to understand otolith formation in Carapus boraborensis. The unusual shape of the otolith is partly explained by the distribution of the epithelium cells, and particularly the sensory epithelium. Experimental evidence shows for the first time that aragonite growth takes place along the c-axis. These aragonite needles present two different habits. On the sulcal side is found the acicular form resulting from rapid growth during a short period of time. On the anti-sulcal side, the prismatic form seen there is due to a slower growth speed over longer periods. The otolith surface was observed each hour during a period of 24h in fishes reared in similar conditions. This allowed for the first time the direct observation on the otolith surface of the deposition of the two layers (L-zone and D-zone). In C. boraborensis, the organic-rich layer (D-zone) develops during the day, whereas the CaCO(3) layer (L-zone) seems to be deposited during the night.

In some Ophidiiform fishes, the anterior part of the swimbladder is thickened into a hard structure called the “rocker bone”, which is thought to play a role in sound production. Although this structure has been described as cartilage or bone, its nature is still unknown. We have made a thorough analysis of the rocker bone in Ophidion barbatum and compared it with both classical bone and cartilage. The rocker bone appears to be a new example of mineralisation. It consists of (1) a ground substance mainly composed of proteoglycans (mucopolysaccharide acid) and fibres and (2) a matrix containing small mineralised spherules composed of a bioapatite and fibrils. These spherules are embedded in mineralised cement of a similar composition to the spherules themselves. The rocker bone grows via the apposition of new apatite spherules at its periphery. These spherules are first secreted by the innermost fibroblast layer of the capsule contained in the rocker bone and then grow extracellularly. Blood vessels, which represent the only means of transport for matrix and mineral material, are numerous. They enter the rocker bone via the hyle and ramify towards the capsule. We propose to call this new kind of mineralised tissue constituting the rocker bone “frigolite” (the Belgian name for styrofoam) in reference to the presence of spherules of different sizes and the peculiarity of the rocker bone in presenting a smooth surface when fractured.

Mesoporous crystalline hematite is a material difficult to prepare by soft-templating with conventional techniques, because of its high crystallization temperature associated to the crystal-to-crystal goethiteto-hematite phase transition. In a previous work, it has been reported that with very careful calcination steps, it is possible to prepare mesoporous hematite films with the spin-coating technique. However, with less conventional techniques such as surfactant-assisted ultrasonic spray pyrolysis, the deposition usually leads to non-porous oxide films or to films with interstitial porosity. In this work, we demonstrate for the first time the proof-of-concept of block-copolymer templating of hematite thin films by the ultrasonic spray pyrolysis technique. Despite the fast thermal decomposition during spray deposition, a regular, monodisperse packing of spherical pores is observed after deposition on pre-heated substrates (250 C) and after a careful post-annealing step at 470 C. Moreover, with the use of a silica scaffold, we successfully preserved porosity up to a temperature as high as 800 C. These films are highly crystalline and they are composed by randomly oriented nanocrystallites with sizes as small as 25 nm. Furthermore, we show that the crystallization evolution with temperature is influenced by the presence of the templating agent and also by the preparation technique.

(Nano)composites based on ethylene vinyl acetate copolymers (EVA) and montmorillonite modified by various alkylammonium cations were processed by mechanical kneading. Polymer intercalation and filler exfoliation were evidenced by X-ray diffraction and transmission electron microscopy, respectively. Nano-composites tensile properties showed that Young's modulus increases significantly even at very low content of the organo-modified filler while preserving high ultimate elongation and tensile stress. The matrix thermal stability in air was increased by 40°C and, interestingly, the obtained nanocomposites present flame retardant properties. TEM micrograph of the nanocomposite based on EVA3 filled with 5 wt.-% of Mont-2CN2C18.

Although Platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative cheaper catalyst materials did not yet yield to equivalent efficiencies. In this work, we tried to understand how to reduce the amount of deposited Pt-material and simultaneously to deliver higher DSC performances. We systematically compared the properties of Pt-counter electrodes prepared by simple solution deposition methods such as spray-coating, dip-coating, brushing with reference to the Pt-electrodes prepared by sputtering onto fluorine doped-tin oxides (FTOs). The morphological and structural characterizations of the deposited Pt-layers were performed by atomic force microscopy (AFM) and scanning electron microscope (SEM). The composition of Pt-material was quantified by using SEM electron dispersive x-ray (EDX) mapping measurements are further compared with optical transmission measurements. Also contact angle and sheet resistance measurements were performed. By taking Pt-layers composition, morphology and structural factors into account 9.16% efficient N3 dye based DSCs were assembled. The DSCs were subjected to various opto-electrical characterization techniques like current-voltage (I-V), external quantum efficiency (EQE), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and transient photo voltage (TPV) measurements. The obtained experimental data suggest that the Pt counter electrodes prepared by solution deposition methods can also reach to high DSC device performances with a consumption of very less amount of Pt material compared with sputtered Pt-layers. This process also proves that higher DSC performances are not limited to the usage of sputtered Pt-layer as counter electrode.

Monolayers of colloidal spheres are used as masks in nanosphere lithography (NSL) for the selective deposition of nanostructured layers. Several methods exist for the formation of the self-organized particles monolayers, among which spin coating appears to be very promising. However, a spin coating process is defined by several parameters like several ramps, rotation speeds and durations. All parameters influence the spreading and drying of the droplet containing the particles. Moreover, scientists are confronted to the formation of numerous defects in spin coated layers, limiting well-ordered areas to a few µm2. So far, empiricism mainly ruled the world of nanoparticles self-organization by spin coating and much of the literature is experimentally based. Therefore, the development of experimental protocols to control the ordering of particles is a major goal for further progress in NSL. We applied experimental design to spin coating, to evaluate the efficiency of this method to extract and model the relationships between the experimental parameters and the degree of ordering in the particles monolayers. A set of experiments was generated by the MODDE software and applied to the spin coating of latex suspension (diam. 490 nm). We calculated the ordering by a homemade image analysis tool. The results of Partial Least Squares (PLS) modeling show that the proposed mathematical model only fits data from strictly monolayers but is not predictive for new sets of parameters. We submitted the data to Principal Component Analysis (PCA) that was able to explain 91% of the results when based on strictly monolayers samples. PCA shows that the ordering was positively correlated to the ramp time and negatively correlated to the first rotation speed. We obtain large defect-free domains with the best set of parameters tested in this study. This protocol leads to areas of 200 µm2, which has never been reported so far.

Nanocomposites based on biodegradable poly(e-caprolactone) (PCL) and layered silicates (montmorillonite) modified by various alkylammonium cations were prepared by melt intercalation. Depending on whether the ammonium cations contain non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions, microcomposites or nanocomposites were recovered as shown by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. The layered silicate PCL nanocomposites exhibited some improvement of the mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as result of a charring effect. This communication aims at reporting that the formation of PCL-based nanocomposites strictly depends on the nature of the ammonium cation and its functionality, but also on the selected synthetic route, i.e. melt intercalation vs. in situ intercalative polymerization. Typically, protonated w-aminododecanoic acid exchanged montmorillonite allowed to intercalate e-caprolactone monomer and yielded nanocomposites upon in situ polymerization, whereas they exclusively formed microcomposites when blended with preformed PCL chains. In other words, it is shown that the formation of polymer layered silicate nanocomposites is not straightforward and cannot be predicted since it strongly depends on parameters such as ammonium cation type and functionality together with the production procedure, i.e., melt intercalation, solvent evaporation or in situ polymerization

Mesoporous templated anatase thin films are very promising materials to act as photoelectrode in dye-sensitized solar cell. Templated-assisted dip-coating techniques are used to obtain thin films with ordered porosity. However, monolayer films are very thin and suffer from a low quantity of active material, leading to poor photovoltaic performances. In this paper, a dip-coating-based multilayer deposition technique is reported. First, we have studied the influence of the template on the film organization and porosity in terms of long-range order, percentage of porosity, pore size and pores connectivity. Different techniques such as transmission electron microscopy (TEM), atmospheric poroellipsometry (AEP) and UV-visible absorption spectroscopy (UV-vis.) have been used to describe the microstructural features of the films with a thickness of 1 µm. The film exhibiting the highest dye loading was selected and its thickness gradually increased up to 4 µm. Finally, the photovoltaic performances of the thick films (1 to 4 µm) have been evaluated in combination with the N-719 dye and show excellent efficiency (6.1%) when compared to values reported in the literature. Such mesostructured films are compared in terms of photovoltaic performance with TiO2 nanoparticles films, generally used in DSSC.

The surface modification of lamellar silica prepared by liquid crystal templating has been investigated. Two hydrophilic surface modifier agents, 2-glycidoxypropyltrimethoxysilane and 2-[methoxy(polyethyleneoxy)propyl)] trimethoxysilane, have been tested. Characterizations of the modified silica include thermal analysis, C-13 and Si-29 solid state NMR, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The different characterizations confirmed the preservation of the lamellar morphology and the Successful surface modification with both silanes along with the template elimination. The results also indicate that the structure and length of the silanes influence the final lamellar organization as well as the grafting yields and mechanisms. (C) 2008 Elsevier Inc. All rights reserved.

We report a study of lamellar silica phase silylation, starting from as-synthesized silica, without the usual heat treatment step. Characterizations of the modified silica include X-ray diffraction, thermal analysis, electron microscopy and solid state NMR. Special attention is given to the possibility of keeping the lamellar organisation along with the elimination of the organic template.

Liquid-state dye-sensitized solar cells can suffer from electrolyte evaporation and leakage. Therefore solid-state hole transporting materials are investigated as alternative electrolyte materials. However, in solid-state dye-sensitized solar cells, optimal TiO2 films thickness is limited to a few microns allowing the adsorption of only a low quantity of photoactive dye and thus leading to poor light harvesting and low conversion efficiency. In order to overcome this limitation, high surface area templated films are investigated as alternative to nanocrystalline films prepared by doctor-blade or screen-printing. Moreover, templating is expected to improve the pore accessibility what would promote the solid electrolyte penetration inside the porous network, making possible efficient charge transfers. In this study, films prepared from different structuring agents are discussed in terms of microstructural properties (porosity, crystallinity) as well as impact on the dye loading and Spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) solid electrolyte filling. We first report Rutherford backscattering spectrometry as an innovative non-destructive tool to characterize the hole transporting materials infiltration. Templated films show dye loading more than two times higher than nanocrystalline films prepared by doctor-blade or screen-printing and solid electrolyte infiltration up to 88%.

Resistivity, thermoelectric power, and thermal conductivity have been measured for a Bi-2212 system synthesized from a glassy precursor, either with a commercially Al2O3 substrate or with a homemade BaZrO3 substrate. Those measurements show that the BaZrO3 substrate gives better superconducting properties to the Bi-2212 than the Al2O3 substrate. The effect of (1.0 T) weak magnetic field has been searched for. The thermal magnetoconductivity and the contributions of the magnetic field to the thermoelectrical power are studied and compared through fine measurements. An electronic contribution seems to appear already well above the critical temperature and to exist up to 200 degrees K. The onset temperature is thus deduced.

La0.6Y0.1Ca0.3MnO3, an ABO(3) perovskite manganite oxide, exhibits a nontrivial behavior in the vicinity of the sharp peak found in the resistivity rho as a function of temperature T in zero magnetic field. The various features seen on drho/dT are discussed in terms of competing phase transitions. They are related to the Mn-O-Mn bond environment depending on the content of the A crystallographic site. A Ginzburg-Landau type theory is presented for incorporating concurrent phase transitions. The specific heat C of such a compound is also examined from 50 to 200 K. A log-log analysis indicates different regimes. In the low temperature conducting ferromagnetic phase, a collective magnon signature (Csimilar or equal toT(3/2)) is found as for what are called magnon-polaron excitations. A Csimilar or equal toT(2/3) law is found at high temperature and discussed in terms of the fractal dimension of the conducting network of the weakly conducting (so-called insulating) phase and an Orbach estimate of the excitation spectral behaviors. The need of considering both independent spin scattering and collective spin scattering is thus emphasized. The report indicates a remarkable agreement for the Fisher-Langer formula, i.e., Csimilar todrho/dT at second order phase transitions. Within the Attfield model, we find an inverse square root relationship between the critical temperature(s) and the total local Mn-O-Mn strain.

A home made experimental set-up allows us to measure the thermal conductivity, the thermopower and the thermal diffusivity simultaneously in the temperature range (20-300 K). Therefore the specific heat can be deduced. The role of a radiation shield is shown to be relevant. Tests of the system are made on a 99.9% pure Cu sample and two polycrystalline cuprate ceramics for illustration. Without any complicated optimisation, the technique indicates much promise already due to its efficiency and rapidity.

Due to their great modularity, ease of implementation, and atom economy, multicomponent reactions (MCRs) are becoming increasingly popular macromolecular engineering tools. In this context, MCRs suitable in polymer synthesis are eagerly searched for. This work demonstrates the potential of the Ugi-three component reaction (Ugi-3CR) for the design of polymers and, in particular, of poly(α-amino amide)s. A series of polymers containing amino and amido groups within their backbone were obtained through a one-pot process by reacting aliphatic or aromatic diamines, diisocyanides, and aldehydes. The impact of temperature, concentration, catalyst loading, and substrates on polymerization efficiency is discussed. A preliminary study on the thermal properties and the solution behavior of these poly(α-amino amide)s was carried out. An aliphatic-rich derivative notably showed some pH-responsiveness in water via protonation−deprotonation of its amino groups.

Radiative lifetimes of seven excited states of Er III have been measured using time-resolved laser-induced fluorescence following two-photon excitation. Relativistic Hartree-Fock calculations taking core-polarization effects into account are found to be in excellent agreement with the experimental results. A large set of new calculated transition probabilities is presented for many transitions of astrophysical interest. These results will be useful for investigating the composition of chemically peculiar stars.

Natural radiative lifetimes of eight levels in Tm III were measured with the time-resolved laser-induced fluorescence (LIF) technique. Free doubly ionized thulium ions were obtained in a laser-produced plasma. Three even-parity levels were excited from the ground state with one-photon excitation, using a laser system generating pulses of 1 ns duration. Five odd-parity levels were excited from the ground state with two-photon excitation, where a picosecond laser system was employed. In both cases, the lifetimes were evaluated from transient LIF signals detected with a fast-detection system. The experimental lifetime results were compared with Hartree–Fock calculations including relativistic corrections. Good agreement was achieved for the 4f126p levels while larger discrepancies are noted for some 4f125d levels.

The local atomic order of semiconducting liquid GeTe is studied using first-principles molecular-dynamics simulations. Our work points out a high degree of alternating chemical order in the liquid and demonstrates the presence of a Peierls distortion close above the melting temperature. This distortion, absent in the high temperature crystalline structure of NaCl type, is a remnant of the atomic arrangement in the A7 low temperature crystalline phase. It disappears slowly with temperature, as the liquid evolves from a semiconducting to a metallic state.

We examine the local atomic order as well as some dynamic properties of the semiconducting liquid GeTe. We employ hot-neutron two-axis diffraction at three temperatures above the melting point and compare these results with ab initio molecular dynamics simulations. The simulations were based on interatomic forces derived from pseudopotentials constructed within density functional theory. At the melting temperature, the Peierls distortion responsible for the lower-temperature crystal phase is shown to manifest itself within the liquid structure. At higher temperatures in the liquid, increasing disorder in the Ge environment determines the eventual semiconductor-metal transition. The calculated kinematic viscosity of the liquid is found to agree with the experimental value and is shown to arise from the small diffusion coefficient of the Te atoms.

The dynamical, dielectric, and elastic properties of GeTe, a ferroelectric material in its low-temperature rhombohedral phase, have been investigated using first-principles density functional theory. We report the electronic energy bands, phonon-dispersion curves, electronic and low-frequency dielectric tensors, infrared reflectivity, Born effective charges, and elastic and piezoelectric tensors and compare them with the existing theoretical and experimental results, as well as with similar quantities available for other ferroelectric materials, when appropriate.

Using first-principles calculations based on density functional theory, we study the properties of germanium telluride crystalline nanoplatelets and nanoparticles. Above a diameter of 2.7 nm, we predict the appearance of polarization vortices giving rise to an unusual ferrotoroidic ground state with a spontaneous and reversible toroidal moment of polarization. We highlight the crucial role of inhomogeneous strain in stabilizing polarization vortices. Combined with the phase-change properties of germanium telluride, the ferrotoroidic properties could be of practical interest for ternary logic applications.

We analyze the structure and dynamics of semiconducting liquid GeSe using ab initio molecular-dynamics simulations. We show the local order of the liquid to be close to that of the low-temperature crystalline phase. alpha -GeSe. In particular, we show that the Peierls distortion, which defines the a phase and vanishes in the high-temperature beta crystalline phase, reenters GeSe in the melt. Examining the distance histograms allows one to analyze the Ge environment as consisting of a Gese(3) unit and having one Ge-Ge defective bond. Evidence is presented that Peierls distortion is directly responsible for the semiconducting behavior of the melt. The calculated viscosity and electrical conductivity are in agreement with the experiment. An additional neutron-diffraction experiment indicates that this liquid structure is unmodified 200 K above the melting point.

Poly(vinylamine) is a highly valuable class of polymer used in several applications. Although free radical polymerization has been extensively exploited for its synthesis, the preparation of poly(vinylamine) with low dispersity and controlled molar mass is barely developed. Recently, a great step was made in this direction via organometallic-mediated radical polymerization (OMRP) of N-vinylacetamides followed by hydrolysis of the pendent amide groups. This chapter summarizes, completes and put in perspective the main accomplishments in the OMRP of acyclic N-vinylamides for the controlled synthesis of both primary and secondary poly(vinylamine)s. Thermal and photochemical initiating systems are compared and the controlled thermally initiated radical polymerization of N-vinylacetamide is reported for the first time. The optimal hydrolysis conditions for producing the poly(vinylamine) derivatives as well as their potential as vectors for gene transfection are also presented.

We successfully prepared NASICON-type Na3V2(PO4)2F3 (NVPF) and a Na3V2(PO4)2F3/carbon nanotubes (CNT) composite by spray-drying followed by heat treatment in argon for 2 hours at 600 °C. The addition of CNT in the spray-drying solution creates a CNT network within the NVPF particles. After grinding, the smaller NVPF particles remain linked by CNT. Thanks to this conducting network, the composite powder displays competitive electrochemical performance when cycled against lithium in hybrid-ion batteries (2–4.6 V vs. Li+/Li) with specific capacities of 125 mAh.g−1 at C/10, 103 mAh.g−1 at 1C and 91 mAh.g−1 at 4C, together with 97.5% capacity retention at 1C over 100 cycles with coulombic efficiency of 99.4%. These results demonstrate that sodium vanadium (III) fluorophosphate electrode material can be obtained in a time-efficient way using the easily up-scalable spray-drying method.

We have studied the influence of the stoichiometry on the structural, magnetic, and magneto-optical properties of bismuth iron garnet (Bi3Fe5O12) thin films grown by pulsed laser deposition. Films with different stoichiometries have been obtained by varying the Bi/Fe ratio of the target and the oxygen pressure during deposition. Stoichiometry variations influence the Curie temperature T-C by tuning the (Fe)-O-[Fe] geometry: TC increases when the lattice parameter decreases, contrary to what happens in the case of stoichiometric rare-earth iron garnets. The thermal variation of the magnetization, the Faraday rotation, and the Faraday ellipticity have been analyzed in the frame of the Neel two-sublattice magnetization model giving energies of -48 K (4.1 meV), -29 K (2.5 meV), and 84 K (7.3 meV) for the three magnetic exchange integrals j(aa), j(dd), and j(ad), respectively. Magneto-optical spectroscopy linked to compositional analysis by Rutherford backscattering spectroscopy shows that Bi and/or Fe deficiencies also affect the spectral variation (between 1.77 and 3.1 eV). Our results suggest that bismuth deficiency has an effect on the magneto-optical response of the tetrahedral Fe sublattice, whereas small iron deficiencies affect predominantly the magneto-optical response of the octahedral sublattice.

We report a detailed set of ac magnetic measurements carried out on bulk large grain La-Ca-Mn-O samples extracted from a floating zone method-grown rod. Three samples with La0.78Ca0.22Mn0.90Ox stoichiometry but differing in their microstructure were investigated by electrical resistivity and ac susceptibility measurements: (i) a single grain sample, (ii) a sample containing two grains, and (iii) a polycrystalline sample. We show that the superimposition of dc magnetic fields during ac magnetic susceptibility measurements is an efficient way for characterizing the magnetic transition of samples with different microstructures. Whereas both single grain and polycrystalline samples display a single susceptibility peak, an additional kink structure is observed in the case of the double grain sample. The temperature dependence of the ac susceptibility measured with superimposed dc magnetic fields is analyzed in the framework of second-order phase transition ideas. The relations between the critical exponents (beta+gamma ~ 1.5, delta ~ 2.5) are found to be close to those of the mean-field model for all samples. This is attributed to the disordering caused by unoccupied Mn sites. ©2003 The American Physical Society.

A hydrothermal synthesis route was used to synthesize iron(III) phosphate hydroxide hydrate–carbon nanotube composites. Carbon nanotubes (CNT) were mixed in solution with Fe1.19(PO4)(OH)0.57(H2O)0.43 (FPHH) precursors for one-pot hydrothermal reaction leading to the FPHH/CNT composite. This produces a highly electronic conductive material to be used as a cathode material for Li-ion battery. The galvanostatic cycling analysis shows that the material delivers a specific capacity of 160 mAh g–1 at 0.2 C (0.2 Li per fu in 1 h), slightly decreasing with increasing current density. A high charge–discharge cyclability is observed, showing that a capacity of 120 mAh g–1 at 1 C is maintained after 500 cycles. This may be attributed to the microspherical morphology of the particles and electronic percolation due to CNT but also to the unusual insertion mechanism resulting from the peculiar structure of FPHH formed by chains of partially occupied FeO6 octahedra connected by PO4 tetrahedra. The mechanism of the first discharge–charge cycle was investigated by combining operando X-ray diffraction and 57Fe Mössbauer spectroscopy. FPHH undergoes a monophasic reaction with up to 10% volume changes based on the Fe3+/Fe2+ redox process. However, the variations of the FPHH lattice parameters and the 57Fe quadrupole splitting distributions during the Li insertion–deinsertion process show a two-step behavior. We propose that such mechanism could be due to the existence of different types of vacant sites in FPHH, including vacant “octahedral” sites (Fe vacancies) that improve diffusion of Li by connecting the one-dimensional channels.

We report a complete procedure to achieve multilayer YBCO thick films by electrophoretic deposition on silver tubes using a suspension of YBCO powder in butanol. With the aim to optimize the magnetic shielding performances of the coatings, we have carried out an extensive investigation of the influence of the deposition parameters, the multilayer deposition sequence and the intermediate/final heat treatments on the coating microstructure. Using the optimized conditions, a 24-layer YBCO coating has been successfully prepared on an 80 mm long Ag tube: the melt growth processed multilayered YBCO thick film thus obtained can shield an applied magnetic field of 1.9 mT at 77 K, the highest value per thickness unit reported so far in the literature for these materials.

The authors report an intriguing resistivity versus magnetic field dependence in polycrystalline composite samples containing a magnetoresistive manganite (ferromagnetic/conducting La0.7Ca0.3MnO3) and a magnetic manganese oxide (ferrimagnetic/insulating Mn3O4). At 10 K, when the magnetic field is scanned from positive to negative values, the resistance peak occurs at positive magnetic field, instead of zero or negative field as usually observed in polycrystalline manganite samples. The position of the resistance peak agrees well with the cancellation of the internal magnetic field, suggesting that the demagnetization effects are responsible for this behavior. (c) 2007 American Institute of Physics.

Electrophoretic deposition (EPD) performance strongly depends on the particles surface chemistry and the ability to manipulate surface–liquid interfaces. In this study an extensive investigation of YBCO suspension in dry acetone, acetone–water mixtures and acetone–iodine is reported. Chemical instability of YBCO particles determines their colloidal behaviour. Charging mechanism of particles has therefore had to be deeply investigated for complete dispersion understanding. In order to determine the conditions of the YBCO suspension stability, measurements of pH, conductivity, zeta-potential, settling tests, modelling of the particle networks and electrophoretic deposition were done. The influence of the water and iodine concentration, and their role as stabilizers was evaluated. Based on experimental results, pair particle potentials were calculated and then different charging mechanisms of YBCO surfaces in acetone were proposed.

LiMn2-xTixO4 compounds with 0.5 =

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