Laboratoire Léon Brillouin

UMR12 CEA-CNRS, Bât. 563 CEA Saclay

91191 Gif sur Yvette Cedex, France

+33-169085241 llb-sec@cea.fr

BD diffusons les neutrons

Faits marquants scientifiques 2022

22 juillet 2022

Fabrizia Foglia, Quentin Berrod, Adam J. Clancy, Keenan Smith, Gérard Gebel, Victoria García Sakai, Markus Appel, Jean-Marc Zanotti, Madhusudan Tyagi, Najet Mahmoudi, Thomas S. Miller, John R. Varcoe, Arun Prakash Periasamy, Daniel J. L. Brett, Paul R. Shearing, Sandrine Lyonnard and Paul F. McMillan

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH− ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100–103 ps) to disentangle the water, polymer relaxation and OH− diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.

https://doi.org/10.1038/s41563-022-01197-2

11 janvier 2022

Philipp Kurzhals, Geoffroy Kremer, Thomas Jaouen, Christopher W. Nicholson, Rolf Heid, Peter Nagel, John-Paul Castellan, Alexandre Ivanov, Matthias Muntwiler, Maxime Rumo, Bjoern Salzmann, Vladimir N. Strocov, Dmitry Reznik, Claude Monney & Frank Weber

Electron-phonon coupling, i.e., the scattering of lattice vibrations by electrons and vice versa, is ubiquitous in solids and can lead to emergent ground states such as superconductivity and charge-density wave order. A broad spectral phonon line shape is often interpreted as a marker of strong electron-phonon coupling associated with Fermi surface nesting, i.e., parallel sections of the Fermi surface connected by the phonon momentum. Alternatively broad phonons are known to arise from strong atomic lattice anharmonicity. Here, we show that strong phonon broadening can occur in the absence of both Fermi surface nesting and lattice anharmonicity, if electron-phonon coupling is strongly enhanced for specific values of electron-momentum, k. We use inelastic neutron scattering, soft x-ray angle-resolved photoemission spectroscopy measurements and ab-initio lattice dynamical and electronic band structure calculations to demonstrate this scenario in the highly anisotropic tetragonal electron-phonon superconductor YNi2B2C. This new scenario likely applies to a wide range of compounds.

https://dx.doi.org/10.1038/s41467-021-27843-y

 

21 avril 2022

Sumit Mehan, Laure Herrmann, Jean-Paul Chapel, Jacques Jestin, Jean-Francois Berret and Fabrice Cousin

We investigate the formation/re-dissociation mechanisms of hybrid complexes made from negatively charged PAA2k coated g-Fe2O3 nanoparticles (NP) and positively charged polycations (PDADMAC) in aqueous solution in the regime of very high ionic strength (I). When the building blocks are mixed at large ionic strength (1 M NH4Cl), the electrostatic interaction is screened and complexation does not occur. If the ionic strength is then lowered down to a targeted ionic strength Itarget, there is a critical threshold Ic = 0.62 M at which complexation occurs, that is independent of the charge ratio Z and the pathway used to reduce salinity (drop-by-drop mixing or fast mixing). If salt is added back up to 1 M, the transition is not reversible and persistent out-of-equilibrium aggregates are formed. The lifetimes of such aggregates depends on Itarget: the closer Itarget to Ic is, the more difficult it is to dissolve the aggregates. Such peculiar behavior is driven by the inner structure of the complexes that are formed after desalting. When Itarget is far below Ic, strong electrostatic interactions induce the formation of dense, compact and frozen aggregates. Such aggregates can only poorly reorganize further on with time, which makes their dissolution upon resalting almost reversible. Conversely, when Itarget is close to Ic more open aggregates are formed due to weaker electrostatic interactions upon desalting. The system can thus rearrange with time to lower its free energy and reach more stable out-of-equilibrium states which are very difficult to dissociate back upon resalting, even at very high ionic strength.

Contact LLB : Fabrice Cousin (LLB/MMB)

 


"The desalting/salting pathway: a route to form metastable aggregates with tuneable morphologies and lifetimes"
S.Mehan, L. Herrmann, J.-P. Chapel, J. Jestin, J.-F. Berret and  F. Cousin, Soft Matter 17 (2021) 8496-8505.

08 février 2022

Les aimants mono-moléculaires suscitent une attention scientifique croissante et ceci depuis trois décennies. Ils diffèrent des aimants métalliques conventionnels par le fait que l'ordre magnétique ne résulte pas d'un ordre à longue distance, mais de la capacité d'alignement de chaque molécule individuelle. L'un des principaux défis dans ce domaine réside dans le contrôle structurel de l'anisotropie magnétique moléculaire qui doit être uni-axiale. Dans cette optique, la technique de diffraction de neutrons polarisés (DNP) développée au laboratoire Léon Brillouin (LLB) offre la possibilité unique de mesurer l’amplitude du moment magnétique et la direction des principaux axes d'anisotropie magnétique d’un ion magnétique par rapport à l'orientation des molécules.

Dans le but d’améliorer les caractéristiques des aimants mono-moléculaires, deux nouveaux complexes iso-structuraux à base de Dy3+ et Ho3+ ont été synthétisés. Ils présentent une forte anisotropie magnétique, avec des barrières de relaxation magnétique respective de 600 K et 270 K. Les mesures réalisées au LLB fournissent la première preuve expérimentale que le composé Dy a une anisotropie magnétique quasi-uniaxiale avec une contribution transverse nulle, alors qu'elle est significative pour le composé Ho, ce qui peut être attribué à l'interaction moins favorable du champ cristallin avec la distribution de charge de l’ion Ho.

 

22 février 2022

J.C.Riedl, M.Sarkar, T.Fiuza, F.Cousin, J.Depeyrot, E.Dubois,G.Mériguet,R.Perzynski and V.Peyre

Some of the most promising fields of application of ionic liquid-based colloids imply elevated temperatures. Their careful design and analysis is therefore essential. We assume that tuning the structure of the nanoparticle-ionic liquid interface through its composition can ensure colloidal stability for a wide temperature range, from room temperature up to 200 °C.

https://doi.org/10.1016/j.jcis.2021.08.017

 

22 juillet 2022

Fabrizia Foglia, Quentin Berrod, Adam J. Clancy, Keenan Smith, Gérard Gebel, Victoria García Sakai, Markus Appel, Jean-Marc Zanotti, Madhusudan Tyagi, Najet Mahmoudi, Thomas S. Miller, John R. Varcoe, Arun Prakash Periasamy, Daniel J. L. Brett, Paul R. Shearing, Sandrine Lyonnard and Paul F. McMillan

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH− ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100–103 ps) to disentangle the water, polymer relaxation and OH− diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.

https://doi.org/10.1038/s41563-022-01197-2

02 juin 2022

Marion Grzelka, Iurii Antoniuk, Éric Drockenmuller, Alexis Chennevière, Liliane Léger, and Frédéric Restagno

The role of the polymer volume fraction, ϕ, on steady-state slippage and interfacial friction is investigated for semi-dilute polystyrene solutions in diethyl phthalate in contact with two solid surfaces. Significant slippage is evidenced for all samples, with slip lengths b obeying a power law dependence. Navier’s interfacial friction coefficient, k, is deduced from the slip length measurements and from independent measurements of the solution viscosity η. The observed scaling of k versus ϕ clearly excludes a molecular mechanism of friction based on the existence of a depletion layer. Instead, we show that the data of η(ϕ) and k(ϕ) are understood when taking into account the dependence of the solvent friction on ϕ. Two models based on the friction of blobs or of monomers on the solid surface well describe our data. Both point out that Navier’s interfacial friction is a semi-local phenomenon.

https://doi.org/10.1021/acs.macromol.0c02804

01 décembre 2022

Déterminer l'interaction à l'origine de la supraconductivité à haute température critique (Tc), découverte en 1986 comme étant une des propriétés majeure des oxydes de cuivre de type cuprate, reste un challenge majeur en physique des solides. Aujourd'hui, des interactions de type magnétique sont plus particulièrement recherchées.

La diffraction de neutrons polarisés a permis de mettre en évidence une structure électronique originale, présentant des boucles de courant avec un ordre spatial complexe, dans la phase "pseudo-gap" d'un de ces supraconducteurs. Cette observation renforce l'idée qu'une interaction magnétique effective issue de la texture magnétique complexe ainsi générée, pourrait être à l'origine de la supraconductivité de ces composés.

07 novembre 2022

Michal Swierczewski, Alexis Chenneviere, Lay-Theng Lee, Plinio Maroni, Thomas Bürgi

Langmuir-Blodgett (LB) technique allows the deposition of gold nanoclusters (atomically precise nanoparticles below 2 nm in diameter) onto solid substrates with an unprecedented degree of control and high transfer ratios. Nanoclusters are expected to follow the crinkle folding mechanism, which promotes the formation of trilayers but kinetically disfavors the formation of the fourth layer. LB films of gold nanoclusters stabilized by thiolated ligand, Au38(SC2H4Ph)24, were prepared at a range of surface pressures in the bilayer/trilayer regime and their internal structure was analyzed with X-ray Reflectivity (XRR) and Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS). Bimodal atomic force microscopy (AFM) imaging was used to quantify the elastic modulus, which can be correlated with the topography at the same point on the surface. Nanocluster bilayers and trilayers exhibited the elastic moduli of ca. 1.2 GPa and 0.9 GPa respectively. Films transferred in the 20-25 mN/m surface pressure regime displayed a particular propensity to form highly vertically organized trilayers. Further compression resulted in disorganization of the layers. Crucially, the use of two cantilevers of contrasting stiffness for bimodal AFM measurements has demonstrated a new approach to quantify the mechanical properties of ultrathin films without the use of deconvolution algorithms to remove the substrate contribution.

https://doi.org/10.1016/j.jcis.2022.10.081

17 octobre 2022

I. Mirebeau et N. Martin, J. Appl. Cryst. (2022). 55, 1173-1183

The application is discussed of neutron methods to the study of reentrant spin glasses (RSGs), close to the transition towards a `canonical' spin glass (SG). The focus is on two emblematic systems, namely Au1−xFex and amorphous a-Fe1−xMnx. A set of experimental results is presented to highlight their peculiar static and dynamic properties. The role of small-angle neutron scattering (SANS) is stressed as an important tool to unravel the structure of these complex systems over mesoscopic length scales. Finally, recent SANS results performed under an applied magnetic field in the region of the RSG → SG transition are presented. They show that vortex-like defects are present in the RSG region up to the critical line and vanish in the SG region. These defects, which develop only in a ferromagnetic medium, could be a key feature to probe the emergence of long-range magnetic order.

23 septembre 2022

Wen-Gen Zheng, Victor Balédent, Claire V. Colin, Françoise Damay, Jean-Pascal Rueff, Anne Forget, Dorothée Colson and Pascale Foury-Leylekian

It has been recently observed that a superconducting phase emerges under pressure in the Fe-based spin-ladders BaFe2X3 (X = S, Se). The low dimensionality of the Fe spin-ladders, which simplifies the elaboration of theoretical models, should help to understand the mechanism of superconductivity. We investigate here the frontier between magnetic and superconducting (SC) phases in BaFe2Se3 by performing challenging powder neutron diffraction (PND) and Fe Kβ x-ray emission spectroscopy (XES) under high pressure. We show that the ambient pressure ground state with a block-like magnetic order is destabilized under pressure. A pressure-induced antiferromagnetic stripe-like spin order, similar to the magnetic order of the parent superconductor BaFe2S3, is observed above 3-4 GPa. Our discovery shows that the stripe magnetic order is a key phase close to the SC dome and its particular magnetic fluctuations could be involved in the stabilization of superconductivity in Fe-based spin ladders.

https://doi.org/10.1038/s42005-022-00955-7

 

02 juin 2022

Marion Grzelka, Iurii Antoniuk, Éric Drockenmuller, Alexis Chennevière, Liliane Léger, and Frédéric Restagno

The role of the polymer volume fraction, ϕ, on steady-state slippage and interfacial friction is investigated for semi-dilute polystyrene solutions in diethyl phthalate in contact with two solid surfaces. Significant slippage is evidenced for all samples, with slip lengths b obeying a power law dependence. Navier’s interfacial friction coefficient, k, is deduced from the slip length measurements and from independent measurements of the solution viscosity η. The observed scaling of k versus ϕ clearly excludes a molecular mechanism of friction based on the existence of a depletion layer. Instead, we show that the data of η(ϕ) and k(ϕ) are understood when taking into account the dependence of the solvent friction on ϕ. Two models based on the friction of blobs or of monomers on the solid surface well describe our data. Both point out that Navier’s interfacial friction is a semi-local phenomenon.

https://doi.org/10.1021/acs.macromol.0c02804

24 mai 2022

Une expérience proposée par des chercheurs de l'Université de l’Académie des sciences chinoise de Pékin en collaboration avec le CEA/Irig/D-Phy/MEM et le LLB révèle que les fluctuations du spin dans un supraconducteur à base de fer ont une direction privilégiée, ce qui suggère un mécanisme potentiel pour la supraconductivité dans ces matériaux.

 

22 février 2022

J.C.Riedl, M.Sarkar, T.Fiuza, F.Cousin, J.Depeyrot, E.Dubois,G.Mériguet,R.Perzynski and V.Peyre

Some of the most promising fields of application of ionic liquid-based colloids imply elevated temperatures. Their careful design and analysis is therefore essential. We assume that tuning the structure of the nanoparticle-ionic liquid interface through its composition can ensure colloidal stability for a wide temperature range, from room temperature up to 200 °C.

https://doi.org/10.1016/j.jcis.2021.08.017

 

01 février 2022

Emil A. Klahn, Andreas M. Thiel, Rasmus B. Degn, Iurii Kibalin, Arsen Gukassov, Claire Wilson, Angelos B. Canaj, Mark Murrie and Jacob Overgaard

We present the magnetic anisotropy of two isostructural pentagonal-bipyramidal complexes, [Ln(H2O)5(HMPA)2]I3·2HMPA (HMPA = hexamethylphosphoramide, Ln = Dy, Ho). Using ac magnetic susceptibility measurements, we find magnetic relaxation barriers of 600 K and 270 K for the Dy- and Ho-compounds, respectively. This difference is supported by polarized neutron diffraction (PND) measured at 5 K and 1 T which provides the first experimental evidence that the transverse elements in the magnetic anisotropy of the Ho-analogue are significant, whereas the Dy-analogue has a near-axial magnetic anisotropy with vanishing transverse contributions. The coordination geometries of the two complexes are highly similar, and we attribute the loss of strong magnetic axiality as expressed in the atomic susceptibility tensors from PND, as well as the smaller relaxation barrier in the Ho-complex compared to the Dy-complex, to the less favorable interaction of the pentagonal bipyramidal crystal field with the characteristics of the Ho(III) 4f-charge distribution.

https://doi.org/10.1039/d1dt01959g

02 septembre 2022

Simeon Minić, Burkhard Annighöfer, Arnaud Hélary, Laïla Sago, David Cornu, Annie Brûlet, Sophie Combet

High pressure (HP) is a particularly powerful tool to study protein folding/unfolding, revealing subtle structural rearrangements. Bovine β-lactoglobulin (BLG), a protein of interest in food science, exhibits a strong propensity to bind various bioactive molecules. We probed the effects of the binding of biliverdin (BV), a tetrapyrrole linear chromophore, on the stability of BLG under pressure, by combining in situ HP small-angle neutron scattering (SANS) and HP-UV absorption spectroscopy. Although BV induces a slight destabilization of BLG during HP-induced unfolding, a ligand excess strongly prevents BLG oligomerization. Moreover, at SANS resolution, an excess of BV induces the complete recovery of the protein “native” 3D structure after HP removal, despite the presence of the BV covalently bound adduct. Mass spectrometry highlights the crucial role of cysteine residues in the competitive and protective effects of BV during pressure denaturation of BLG through SH/S-S exchange.

https://doi.org/10.1016/j.bpj.2022.06.003

A presentation in French on Scoop.it! of the Paris-Saclay University.

24 août 2022

Le rôle régulateur de la protéine Hfq, protéine bactérienne notamment trouvée chez Escherichia coli, est attribué principalement à sa fonction d'ARN-chaperon, facilitant les interactions entre ARNs. La protéine est aussi impliquée dans la structuration et la compaction de l’ADN.

Une large collaboration internationale a étudié par diverses techniques d'imagerie et de spectroscopie, en particulier sur synchrotron, les complexes formés par la protéine amyloïde Hfq et l'ADN simple brin. Il est ainsi montré que la protéine Hfq peut jouer un rôle dans la recombinaison génétique et la réplication.

28 novembre 2022

H. P. Khanh Ngo, E. Planes, C. Iojoiu, P. Soudant, A.-L. Rollet, P. Judeinstein

The increasing need of portable electrical resources requires to develop post-Li batteries, in which redox reactions are then based on the different alkali or earth alkaline ions. Keeping in mind the specific advantages of electrolytes based on ionic liquid (electrochemical properties, safety, stability …), this paper focuses on the specific properties of those obtained by mixing alkali or earth alkaline salts (Li+, Na+, K+, Cs+ and Mg2+) in a prototypical ionic liquid, the 1-butyl-3-methyl imidazolium bis(trifluoromethyl sulfonyl) imide (BMImTFSI). Transport properties of these electrolytes are deciphered from viscosity, ionic conductivity and individual self-diffusion coefficients. At room temperature, change of electrolyte composition (nature of ion, concentration) induces some large variations of these transport properties. However, if these measurements are scaled towards glass transition temperatures, master curves are obtained with only slight differences between monovalent alkali and divalent earth alkaline ions. Further information is obtained from the Walden approach and evidences that these electrolytes are ’good ionic conductors’. These results are confirmed from self-diffusion coefficients which also allows to retrieve contributions of each species to ionic transport and then dissociation ratio inside these mixtures. Slight differences between alkali and earth alkali ions may be related to solvation mechanisms, as proposed from infrared spectroscopy measurements.

https://doi.org/10.1016/j.jil.2022.100044

 

11 août 2022

E. Kume and L. Noirez

We show that a confned viscous liquid emits a dynamic thermal response upon applying a low frequency (∼1 Hz) shear excitation. Hot and cold thermal waves are observed in situ at atmospheric pressure and room temperature, in a viscous liquid (polypropylene glycol) at various thicknesses ranging from 100 µm up to 340 µm, upon applying a mechanical oscillatory shear strain. The observed thermal efects, synchronous with the mechanical excitation, are inconsistent with a viscous behaviour. It indicates that mesoscopic liquids are able to (partly) convert mechanical shear energy in non-equilibrium thermodynamic states. This efect called thermo-elasticity is well known in solid materials. The observation of a thermal coupling to the mechanical shear deformation reinforces the assumption of elastically correlated liquid molecules. The amplitude of the thermo-elastic waves increases linearly by increasing the shear strain amplitude up to a transition to a non-linear thermal behavior, similar to a transition from an elastic to plastic regime. The thermo-elastic efects do not give rise to any change in stress measurements and thus the dynamic thermal analysis provides unique information about dynamic liquid properties.
 

https://doi.org/10.1515/jnet-2021-0091

01 juillet 2022

Tiago Outerelo Corvo, Antoine Jourdain, Shona O’Brien, Frédéric Restagno, Eric Drockenmuller, and Alexis Chennevière

Poly(ionic liquid)s (PILs), similar to their ionic liquid (IL) analogues, present a nanostructure arising from local interactions. The influence of this nanostructure on the macromolecular conformation of polymer chains is investigated for the first time by means of an extensive use of small-angle neutron scattering on a series of poly(1-vinyl-3-alkylimidazolium)s with varying alkyl side-chain length and counter-anion, both in bulk and in dilute solutions. Radii of gyration are found to increase with the side-chain length in solution as a consequence of crowding interactions between neighboring monomers. In bulk, however, a nonmonotonic evolution of the radius of gyration reflects a change in chain flexibility and a potential screening of electrostatic interactions. Additionally, at a smaller scale, SANS provides an experimental estimation of both the chain diameter and the correlation length between neighboring chains, comparison of which unveils clear evidence of interdigitation of the alkyl side chains. These structural features bring precious insights into the understanding of the dynamic properties of PILs.

https://doi.org/10.1021/acs.macromol.2c00290

21 avril 2022

Sumit Mehan, Laure Herrmann, Jean-Paul Chapel, Jacques Jestin, Jean-Francois Berret and Fabrice Cousin

We investigate the formation/re-dissociation mechanisms of hybrid complexes made from negatively charged PAA2k coated g-Fe2O3 nanoparticles (NP) and positively charged polycations (PDADMAC) in aqueous solution in the regime of very high ionic strength (I). When the building blocks are mixed at large ionic strength (1 M NH4Cl), the electrostatic interaction is screened and complexation does not occur. If the ionic strength is then lowered down to a targeted ionic strength Itarget, there is a critical threshold Ic = 0.62 M at which complexation occurs, that is independent of the charge ratio Z and the pathway used to reduce salinity (drop-by-drop mixing or fast mixing). If salt is added back up to 1 M, the transition is not reversible and persistent out-of-equilibrium aggregates are formed. The lifetimes of such aggregates depends on Itarget: the closer Itarget to Ic is, the more difficult it is to dissolve the aggregates. Such peculiar behavior is driven by the inner structure of the complexes that are formed after desalting. When Itarget is far below Ic, strong electrostatic interactions induce the formation of dense, compact and frozen aggregates. Such aggregates can only poorly reorganize further on with time, which makes their dissolution upon resalting almost reversible. Conversely, when Itarget is close to Ic more open aggregates are formed due to weaker electrostatic interactions upon desalting. The system can thus rearrange with time to lower its free energy and reach more stable out-of-equilibrium states which are very difficult to dissociate back upon resalting, even at very high ionic strength.

Contact LLB : Fabrice Cousin (LLB/MMB)

 


"The desalting/salting pathway: a route to form metastable aggregates with tuneable morphologies and lifetimes"
S.Mehan, L. Herrmann, J.-P. Chapel, J. Jestin, J.-F. Berret and  F. Cousin, Soft Matter 17 (2021) 8496-8505.

21 avril 2022

Sumit Mehan, Laure Herrmann, Jean-Paul Chapel, Jacques Jestin, Jean-Francois Berret and Fabrice Cousin

We investigate the formation/re-dissociation mechanisms of hybrid complexes made from negatively charged PAA2k coated g-Fe2O3 nanoparticles (NP) and positively charged polycations (PDADMAC) in aqueous solution in the regime of very high ionic strength (I). When the building blocks are mixed at large ionic strength (1 M NH4Cl), the electrostatic interaction is screened and complexation does not occur. If the ionic strength is then lowered down to a targeted ionic strength Itarget, there is a critical threshold Ic = 0.62 M at which complexation occurs, that is independent of the charge ratio Z and the pathway used to reduce salinity (drop-by-drop mixing or fast mixing). If salt is added back up to 1 M, the transition is not reversible and persistent out-of-equilibrium aggregates are formed. The lifetimes of such aggregates depends on Itarget: the closer Itarget to Ic is, the more difficult it is to dissolve the aggregates. Such peculiar behavior is driven by the inner structure of the complexes that are formed after desalting. When Itarget is far below Ic, strong electrostatic interactions induce the formation of dense, compact and frozen aggregates. Such aggregates can only poorly reorganize further on with time, which makes their dissolution upon resalting almost reversible. Conversely, when Itarget is close to Ic more open aggregates are formed due to weaker electrostatic interactions upon desalting. The system can thus rearrange with time to lower its free energy and reach more stable out-of-equilibrium states which are very difficult to dissociate back upon resalting, even at very high ionic strength.

Contact LLB : Fabrice Cousin (LLB/MMB)

 


"The desalting/salting pathway: a route to form metastable aggregates with tuneable morphologies and lifetimes"
S.Mehan, L. Herrmann, J.-P. Chapel, J. Jestin, J.-F. Berret and  F. Cousin, Soft Matter 17 (2021) 8496-8505.

22 février 2022

J.C.Riedl, M.Sarkar, T.Fiuza, F.Cousin, J.Depeyrot, E.Dubois,G.Mériguet,R.Perzynski and V.Peyre

Some of the most promising fields of application of ionic liquid-based colloids imply elevated temperatures. Their careful design and analysis is therefore essential. We assume that tuning the structure of the nanoparticle-ionic liquid interface through its composition can ensure colloidal stability for a wide temperature range, from room temperature up to 200 °C.

https://doi.org/10.1016/j.jcis.2021.08.017

 

23 mars 2022

Christiane Alba-Simionesco , Patrick Judeinstein , Stéphane Longeville, Oriana Osta , Florence Porcher , Frédéric Caupin , and Gilles Tarjus

The proneness of water to crystallize is a major obstacle to understanding its putative exotic behavior in the supercooled state. It also represents a strong practical limitation to cryopreservation of biological systems. Adding some concentration of glycerol, which has a cryoprotective effect preventing, to some degree, water crystallization, has been proposed as a possible way out, provided the concentration is small enough for water to retain some of its bulk character and/or for limiting the damage caused by glycerol on living organisms. Contrary to previous expectations, we show that, in the “marginal” glycerol molar concentration ≈ 18%, at which vitrification is possible with no crystallization on rapid cooling, water crystallizes upon isothermal annealing even below the calorimetric glass transition of the solution. Through a time-resolved polarized neutron scattering investigation, we extract key parameters, size and shape of the ice crystallites, fraction of water that crystallizes, and crystallization time, which are important for cryoprotection, as a function of the annealing temperature. We also characterize the nature of the out-of-equilibrium liquid phases that are present at low temperature, providing more arguments against the presence of an isocompositional liquid–liquid transition. Finally, we propose a rule of thumb to estimate the lower temperature limit belowwhich water crystallization does not occur in aqueous solutions.

https://doi.org/10.1073/pnas.2112248119

23 septembre 2022

Wen-Gen Zheng, Victor Balédent, Claire V. Colin, Françoise Damay, Jean-Pascal Rueff, Anne Forget, Dorothée Colson and Pascale Foury-Leylekian

It has been recently observed that a superconducting phase emerges under pressure in the Fe-based spin-ladders BaFe2X3 (X = S, Se). The low dimensionality of the Fe spin-ladders, which simplifies the elaboration of theoretical models, should help to understand the mechanism of superconductivity. We investigate here the frontier between magnetic and superconducting (SC) phases in BaFe2Se3 by performing challenging powder neutron diffraction (PND) and Fe Kβ x-ray emission spectroscopy (XES) under high pressure. We show that the ambient pressure ground state with a block-like magnetic order is destabilized under pressure. A pressure-induced antiferromagnetic stripe-like spin order, similar to the magnetic order of the parent superconductor BaFe2S3, is observed above 3-4 GPa. Our discovery shows that the stripe magnetic order is a key phase close to the SC dome and its particular magnetic fluctuations could be involved in the stabilization of superconductivity in Fe-based spin ladders.

https://doi.org/10.1038/s42005-022-00955-7

 

22 juillet 2022

Fabrizia Foglia, Quentin Berrod, Adam J. Clancy, Keenan Smith, Gérard Gebel, Victoria García Sakai, Markus Appel, Jean-Marc Zanotti, Madhusudan Tyagi, Najet Mahmoudi, Thomas S. Miller, John R. Varcoe, Arun Prakash Periasamy, Daniel J. L. Brett, Paul R. Shearing, Sandrine Lyonnard and Paul F. McMillan

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH− ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100–103 ps) to disentangle the water, polymer relaxation and OH− diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.

https://doi.org/10.1038/s41563-022-01197-2


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