Title:Effects of confinement on inhomogeneous systems.
Starting date: 01/01/2017 Project duration: 60 month Call (part) identifier: H2020-MSCA-RISE-2016 Topic: MSCA-RISE-2016
Research and Innovation Staff Exchange Fixed EC Keywords: Phase transitions, phase equilibria, Statistical physics (condensed matter), Soft condensed matter Free keywords: inhomogeneous systems, confinement, self-assembly, ionic systems Summary: The objective of the project is determination of universal features and specific properties of various systems spontaneously ordering into spatially inhomogeneous structures (mobile ions in solids, ionic liquid mixtures, soft- matter and biological systems), with special focus on effects of confinement. There is striking similarity between properties of the above systems despite different interactions and length scales of inhomogeneities. The fundamental relation between structural inhomogeneities and mechanical and thermodynamic properties is not fully understood because the exchange of knowledge between the solid-state, liquid-matter, soft-matter and biophysical communities is limited. Theoretical and simulation approaches developed by 3 EU MS + 1 AC + 2 TC groups are closely connected or complementary. We use mean-field, liquid-matter, DFT, integral equations, field and collective-variables theories, molecular simulation approaches, and experimental methods of electrochemistry. We will share our experience in constructing/modifying, solving and verifying experimentally models for different complex systems. The new results and theoretical approaches will help in future studies of various inhomogeneous systems. The first work package concerns systems spontaneously forming ordered patterns, from thin films on solid surfaces through particles on interfaces to biological membranes and arid ecosystems. The pattern formation can be exploited in innovative technology. In the second work package we will investigate ionic liquids/ionic-liquid mixtures, especially near charged surfaces and in porous media, and mobile ions in intercalation compounds. Mobile ions and ionic liquids in porous electrodes are potentially important in innovative electrochemistry. EU/TC knowledge transfer will be by joint theoretical, simulation and experimental studies. Open workshops will be organized. Long term visits of young researchers and joint supervision of PhD students are planned.
Beneficiaries
Institute of Physical Chemistry, Warsaw, Poland (Project Coordinator)
The host organization of the IPC team is the Institute of Physical Chemistry of the Polish Academy of Sciences in Warsaw (HR Excellence in Research). The research work is carried out in 8 departments and 31 research teams working in solid state and surface physics and chemistry, soft matter, electrochemistry, photochemistry and photophysics, supramolecular and synthetic chemistry, and statistical thermodynamics of complex systems. For our theoretical work the necessary infrastructure are two clusters composed of several multiprocessor servers and workstations that belong to IPC and will be at the disposal of the visitors.
Group leader:Alina Ciach
Agencia Estatal Consejo Superior de Investigaciones Cientificas, Madrid, Spain
The host organization of the CSIC team is the Institute of Physical Chemistry Rocasolano (IQFR), a research center which hosts four departments, a total of 35 senior scientists and 20 technicians, together with approximately 30 PhD students and postdoctoral researches. With an average of 150-200 publications in high impact journals IQFR is one of the main research centers in the area of Chemistry in the CSIC. The CSIC as a whole ranks as one of the largest and most productive institutions in Europe after MPG and CNRS. The areas of research at the IQFR move in the boundaries of Biology, Physics and Chemistry. Concerning facilities relevant for the CONIN consortium, the IQFR has a cluster for parallel computation with 512 cores interconnected with Infiniband, and 5 nodes with GPU computing capabilities that will be at the disposal of the visitors.
Group leader:Eva Noya
Institute for Condensed Matter Physics, Lviv, Ukraine
The host organization of the ICMP team is the Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine (Lviv, Ukraine). The research areas of the institute are statistical theory of solids and soft matter, computer modelling of physical processes and evaluation of basic physical characteristics of condensed and complex systems. The institute publishes approximately 100 original papers every year. The group members have experience of scientific collaboration with more than 50 research centers throughout the world. The computer cluster of ICMP is based on 24 multiprocessor nodes with 220 CPU cores totally (the peak performance of the cluster is estimated about 2TFlops) and will be at the disposal of the visitors. The ICMP cluster is a part of European Grid Infrastructure (EGI). The institute is a founder of the international scientific journal “Condensed Matter Physics” which since 2005 has been included into the Thomson Reuters Master Journal List.
Group leader:Oksana Patsahan
Ecole Nationale Superieure de Chemie de Paris, et Universite Pierre et Marie Curie - Paris 6, France
The host organization of the CPT team is Chimie ParisTech, which is the major engineer school for chemistry in France created in 1896 by Charles Friedel and one of the directors Henri Moissan obtained Nobel price in chemistry. The school hosts 320 engineering students, 120 PhD student, 40 Post Doc, 120 between teachers and researchers, with about 250 publications and 5 to 10 patents per year. It offers courses in all domains of chemistry. The research is divided into three main structures. In the Institute of Research of Chimie Paris (IRCP) involved in the project, the research covers a broad range of topics in chemical and physicochemical sciences from the fundamentals to the applications. CPT is a member of MESO PSL group, this gives access to large parallel computers that will be at the disposal of the visitors. A large access to experimental techniques for synthesis and characterization are available (XPS, DRX, TEM, FEGSEM etc.).
Group leader:Dung di Caprio
Partners
University of La Plata, Argentina
The host organization of the UNLP team is the Instituto de Física de Líquidos y Sistemas Biológicos (IFLYSIB). IFLYSIB has a joint dependence with Universidad Nacional de La Plata (UNLP) and Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). 26 researchers, 12 PhD students (3 of them from Latin American countries), and 2 Post Doctoral researchers work in this institution. Research is mainly focused on theoretical studies in condensed soft matter (numerical simulations, confined fluids, complex systems,..), and structure and function of biomolecules. Experimental works are carried out on highly correlated systems at low temperatures, and transport phenomena in collagen membranes. The computer facility consists of a cluster of 250 processors, and full access to Internet and to Biblioteca Electrónica de Ciencia y Tecnología (17000 journals, 9000 books) is available, all in a pleasant and quiet work environment in a 20th century mansion.
Group leader:Guillermo Zarragoicoechea
Belorussian State Technological University, Minsk, Belarus
The host organization of the BSTU team is the Chemical Technology and Engineering Faculty at the Belorussian State Technological University in Minsk, which is the major engineer school for chemistry in Belarus. It offers courses which cover all domains of chemistry. It hosts more than 10 000 undergraduate students, more than 100 PhD students, 290 professors (45 full professors among them), about 400 candidates of science (PhDs). The University publishes the scientific journal Trudy BSTU in 8 issues every year that cower all the scientific activities of the University staff. The most important studies are published in high ranking international journals. The University maintains scientific contacts with many scientific centers and universities throughout the world. The group members are experienced in thermodynamics and statistical mechanics of condensed matter, investigation of energy redistribution in water and some organic molecules, electronic processes in photovoltaic systems, application of lattice fluid models for investigating phase transformations, equilibrium properties and diffusion processes of solid state ionics, surface monolayers, and intercalation compounds. The electrochemistry department is equipped with the potentsiostat-galvanostat Autolab 302N with modules FRA 32m, EQCM, ADC64, SCAN250, Dac164, the current source KRAFT Klex, Microhardnessmeter AFFRI-MVDM8, the automatic titrators Titroline Easy, potentsiostat-galvanostats IPC PRO2, IPC PROM etc. that will be at the disposal of the visitor from CPT.
Group leader:Vyacheslav S. Vikhrenko
Work Packages
This project consists of four work packages. The scientific work packages are
The remaining work packages are (WP3) communication, dissemination and transfer of knowledge and (WP4) coordination and management.
The figure below shows how various groups are involved in work packages WP1 and WP2. Scientific work packages WP1,2 and the groups involved in the corresponding research (left) and the planned secondments (right). Top row: our plans. Bottom row: our realization
Work Package #1: Modeling of self-assembly in systems with competing interactions
Objectives:
To gain fundamental knowledge about universal and specific properties of self-assembling systems, with a special focus on the effects of confinement. In particular, structure, thermodynamic and mechanical properties of various model systems with competing interactions in single compartments with different types of walls and in porous media will be described. Younger researchers will learn advanced theoretical and simulation methods during long-term visits to IPC and CSIC.
Phase diagram in block-copolymers (left) and in colloidal systems with the SALR potential (right) In the left panel the horizontal axis is the length ratio of the A and B chains and the vertical one is inversely proportional to temperature T. In the right panel the horizontal and vertical axes are dimensionless density of particles and T respectively. The surfaces in the right panel enclose regions with excess (depleted) density for the average density smaller (greater) than 0.25 (Ciach et. al. 2013). Results of the IPC group.
Left column: Two species SALR particles forming patterns on the surface of a spherical nanoparticle (Meyra et al 2010). Central column: Monte Carlo simulations on SALR interacting individuals showing pattern formation similar to that observed in stressed ecosystems. Views are in perspective (Meyra et al 2012 and 2015). Right column: Field observations. (A to C) Arid ecosystems: (A) Labyrinth of bushy vegetation in Niger; (B) Striped pattern of bushy vegetation in Niger; (C) Labyrinth of perennial grass Paspalum vaginatum in Israel. (D and E) Savanna ecosystems: Aerial and ground photographs of spots of tree patches in Ivory Coast and French Guiana, respectively. (F and G) Peatlands: Regular maze patterns of shrubs and trees in western Siberia. Results of the UNLP group.
Work Package #2: Modeling of systems with dominant electrostatic interactions
Objectives: To extend our knowledge on ionic systems in bulk and at interfaces, specifically in disordered porous media in the regions of large concentration gradients. Various models and confinements will be considered.
Chemical and molecular structures of some ionic liquids and their coarse-grained representation
Model of an ionic liquid (blue and red particles) confined in disordered porous matrices formed by immobilized spherocylinders (grey particles) with different orientation (nematic) ordering.
Workshops
Jablonna Palace, Warsaw, 17-20.02.2017
Our first workshop was held in Jablonna Palace in Warsaw in 2017. The aim of the workshop was to summarize the recent progress in colloidal and amphiphilic self-assembly and in the room temperature ionic liquids, both in the bulk and in confinement, as well as in mobile ions in intercalation compounds and on solid surfaces. Recent advances in theoretical and simulation methods appropriate for inhomogeneous systems, and in experimental studies of such systems were presented. Outstanding invited theoreticians and experimentalists as well as senior researchers participating in the project delivered review lectures, while younger participants presented posters during two poster sessions. Important open questions were discussed at a round-table closing the workshop.
The official web page of this CONIN workshop is here.
In addition to exciting invites lectures and presentations by CONIN members (the slides will be added later), we had a mid-term meeting with our EC Project Officer Dr. Amanda Jane Ozin-Hofsaess (here is the program). The progress report presented on the meeting by the coordinator Professor Alina Ciach can be downloaded here. The discussions were very fruitful and Amanda Jane gave her personal feedback as "outstanding" progress in this social media .
The official web page of this CONIN workshop is here.
ICMP, Lviv, 1-2.06.2019
The third workshop was on systems with competing electrostatic and short-range interactions and was organized as a satellite meeting of StatyPhys2019.
The official web page of this CONIN workshop is here . The program and some presentations can be downloaded as a single PDF file.
Warsaw, 07-10.06.2022, Complex interactions, clustering, swarming and effects of confinement
The official web page of this CONIN workshop is here.
Summary
We have developed new theoretical methods and simulation procedures for systems with spontaneous inhomogeneities on different length scales or with hyperuniformity. With these new methods, we investigated well-established and new models of:
Concentrated ions in different solvents and in solids
Core-shell particles
Charged particles with effective short-range attraction and
Mixtures of such particles
We determined thermodynamic, structural, electrostatic and kinetic properties of the above systems in bulk and in confinement on flat or curved surfaces, in single pores with different sizes and shapes as well as in various ordered and disordered porous materials.
Representative configuration in a mixture with competing interactions (a). Formation of chiral structures by self-assembled aggregates of particles in different confinement (b)-(d)
For particles with short-range attraction long-range repulsion (SALR) we discovered in particular:
Anomalous decrease of adsorption from bulk reservoir for increasing gas pressure when clusters dominate in bulk
Chains of clusters in dilute- and alternating layers of particles in a mixture of SALR particles with particular cross-interaction (Fig.6a)
Thick dense layer with particles forming ordered patterns adsorbed on a selective surface from a dilute mixture of SALR particles
Formation of chiral structures made by worm-like clusters in pipes with different cross-section (Fig.6c), spherical shells (Fig. 6d) or inside a hexagon with a small obstacle attached to a vertex (Fig.6b)
Formation of new ordered patterns by SALR particles inside ordered porous materials (Fig.7)
Appearance of disordered hyperuniformity in mixtures of dipolar particles that can lead to invisible materials.
New ordered patterns formed by SALR particles inside ordered porous materials
For core-shell particles we predicted formation of many regular patterns on a fluid interface and a strong dependence of the number and the type of the patterns on the thickness of the polymeric shell and on cross-linking distribution. The sensitivity to the details of the interactions is in strong contrast to the universal behavior of the SALR particles and block copolymers.
Using the new theories for ionic systems we have determined
Strong effect of the demixing phase transition in mixtures of ionic liquid and neutral solvent on capacitance of the double layer (Fig.8a)
Jumps of the stored energy at the ionization/deionization transition in slits (Fig.9)
Phase transitions of ionic liquids and ionic liquid mixture with anisotropic solvent confined in porous medium (Fig.8b)
Distribution of ions and electrostatic potential in ionic liquids, ionic liquid mixtures and solid electrolyte near a charged surface and between flat electrodes
The effect of finite pore length on ion structure and charging
The effect of the crystal field variation on the screening effects and electro-physical characteristics.
Strong effect of the proximity to the demixing phase transition in mixtures of ionic liquid and neutral solvent on capacitance of the double layer (a). Representative configuration of ionic liquid mixture with anisotropic solvent confined in porous medium (b).
Cartoon showing jumps of the stored energy at the ionization/deionization transition in slits
Progress beyond the state of the art:
We have shown how the size and shape of the confining walls can modify the patterns formed by the particles and induce patterns absent in bulk. Our new theories and computer simulations will be used in continuing studies of inhomogeneous or hyperuniform systems that are ubiquitous in soft- and living matter. Experimental studies of nanoparticles production and their assembly during formation of nanostructured surfaces can find applications in anti-corrosion coatings.
We have developed new theoretical approaches and simulation procedures suitable for inhomogeneous systems, and introduced several new models. We have obtained numerous results concerning phase transitions and effects of confinement, and discovered new phenomena, such as:
anomalous adsorption in cluster-forming systems that may play an important role for implants
new ordered structures self-assembled in various types of confinement or by core-shell particles that may guide tailored patterns for different smart materials
new shape of the capacitance curve close to the phase separation having strong effect on the energy and charge storage
disordered hyperuniformity in mixtures of dipolar particles on a surface that may lead to invisible materials.
G. Bokun, I. Kravtsiv, M. Holovko, V. Vikhrenko, D. di Caprio, Short- and long-range contributions to equilibrium and transport properties of solid electrolytes, Condensed Matter Physics, 25, 194505 (2021) .
H. Pianka, S. Falah, S. Zanna, V. Bezborodov, S. Mikhalyonok, N. Kuz’menok, A. Chernik, Y. Xue and A. Taleb , Anticorrosion Efficiency of Inhibitor Coatings Based on Ammonium Cation with Different Substituents: The Influence of Wettability and Molecular Structure, Coatings , 11, 12, 1512, (2021) .
W. Luo, A. Taleb, Large-Scale Synthesis Route of TiO2 Nanomaterials with Controlled Morphologies Using Hydrothermal Method and TiO2 Aggregates as Precursor, Nanomaterials, 11, 2, 365 (2021) .
S. Mehraz, W. Luo, J. Swiatowska, B. Bezzazi, A. Taleb, Hydrothermal Synthesis of TiO2 Aggregates and Their Application as Negative Electrodes for Lithium-Ion Batteries: The Conflicting Effects of Specific Surface and Pore Size, Materials, 14, 4, 916 (2021) .
Z. Ait-Touchente, S. Falah, E. Scavetta, M. M. Chehimi, R. Touzani, D. Tonelli and A. Taleb, Different Electrochemical Sensor Designs Based on Diazonium Salts and Gold Nanoparticles for Picomolar Detection of Metals, Molecules, 25, 17, 3903 (2020) .
E. Lomba, J. J. Weis, L. Guisández, S. Torquato, Minimal statistical-mechanical model for multihyperuniform patterns in avian retina, Physical Review E, 102, 012134 (2020).
V Grishina, V Vikhrenko, A Ciach, Structural and thermodynamic peculiarities of core-shell particles at fluid interfaces from triangular lattice models, Entropy 22 (11), 1215 (2020).
H. Serna, E. Noya and W.T. Gozdz, The influence of confinement on the structure of colloidal systems with competing interaction, Soft Matter (2020).
E. Bildanau, J. Pekalski, V. Vikhrenko and A. Ciach, , Adsorption anomalies in a 2D model of cluster-forming systemsPhys. Rev. E., 101, 012801 (2020) .
G. Bokun, I. Kravtsiv, M. Holovko, V. Vikhrenko, D. di Caprio , Short- and long-range contributions to equilibrium and transport properties of solid electrolytes, Cndensed Matter Physics, 22, No. 3, 33501:1-14 (2019).
T. Patsahan, G. Bokun, D. di Caprio, M. Holovko, and V. Vikhrenko, The effect of short-range interaction and correlation on the charge and electric field distribution in a model solid electrolyte, Solid State Ionics, 335, 156-163 (2019).
Carolina Cruz, Svyatoslav Kondrat, Enrique Lomba, and Alina Ciach, Effect of proximity to ionic liquid-solvent demixing on electrical double layers, Journal of Molecular Liquids, 294, 111368 (2019) .
Ariel G. Meyra, Guillermo J. Zarragoicoechea, Alberto. L. Maltz, Enrique Lomba and Salvatore Torquato, Hyperuniformity on spherical surfaces, Physical Review E, 100, 24700045 (2019).
J. Pekalski, E. Bildanau and A. Ciach, Self-assembly of spiral patterns in confined system with competing interactions, Soft Matter, 15, 7715 (2019).
V. V. Ignatyuk, I. M. Mryglod, T. Bryk, A simple ansatz for the study of velocity autocorrelation functions in fluids at different timescales
, Condensed Matter Physics 21,1. (2018)
Ya. G. Groda, V.S. Vikhrenko, D. di Caprio, Equilibrium properties of the lattice
system with SALR interaction potential on a square lattice: quasi-chemical approximation versus Monte Carlo simulation, arXiv:1812.08526.
K. Breitsprecher, C. Holm, S. Kondrat, Charge Me Slowly, I Am in a Hurry:
Optimizing Charge–Discharge Cycles in Nanoporous Supercapacitors, ACS Nano 12 (10), 9733-9741 (2018).
M. Hvozd, T. Patsahan, M. Holovko, Isotropic-nematic transition and demixing
behaviour in binary mixtures of hard spheres and hard spherocylinders confined in a disordered porous medium: Scaled particle theory, J. Phys. Chem. B 122, 5534-5546 (2018).
O.V. Patsahan, T.M. Patsahan, M.F. Holovko, Vapour-liquid critical parameters of a
2:1 primitive model of ionic fluids confined in disordered porous media, J. Mol. Liq. 270, 97-105 (2018).
O.V. Patsahan, T.M. Patsahan, M.F. Holovko, Vapor-liquid phase behavior of a size-
asymmetric model of ionic fluids confined in a disordered matrix: The collective-variables based approach, Phys. Rev. E 97, 022109 (2018).
V. V. Ignatyuk, I. M. Mryglod, T. Bryk, A simple closure procedure for the study of velocity autocorrelation functions in fluids as a “bridge” between different theoretical approaches
, Journal of Chemical Physics, 149 , 054101. (2018)
Y. V. Kalyuzhnyi; M. Holovko; J. Reščič; P. T. Cummings, Primitive models of room
temperature ionic liquids. Liquid-gas phase coexistence, J. Mol. Liq. 270, 7-13.
H. Serna, E. G. Noya and W.T. Góźdź, Assembly of helical structures in
systems with competing interactions under cylindrical confinement, Langmuir, doi:10.1021/acs.langmuir.8b03382 .
M. Holovko, T. Patsahan, and W. Dong, On the improvement of SPT2 approach in the
theory of a hard sphere fluid in disordered porous media, Condens. Matter Phys. 20, 33602 (2017).
M.F. Holovko, M.V. Hvozd, Isotropic-nematic mixture of hard spheres and hard
spherocylinders: scaled particle theory description,Condens. Matter Phys. 20, 43501 (2017) .
P. Argyrakis, P. Giazitzidis, L. Skarpalezos, Y. G. Groda, V. S. Vikhrenko, Influence of Obstacles on Equilibrium Properties of the Lattice Fluid on a Surface. Proceedings of the 2017 IEEE 7 th International Conference on Nanomaterials: Applications & Properties (NAP-2017). Part 1. Paper 01PCSI15 (5 p.) doi: 10.1109/NAP.2017.8190152 (INSPEC Accession Number: 17418886).
Yaroslav Groda, Eldar Bildanov, and Vyacheslav Vikhrenko Thermodynamic Properties of the System with Competing Interactions on a Triangular Lattice Proceedings of the 2017 IEEE 7th International Conference on Nanomaterials: Applications & Properties (NAP-2017). Part 3. Paper 03NNSA31 (5p). doi: 10.1109/NAP.2017.8190275 (INSPEC Accession Number: 17418845).
Yaroslav Groda, Eldar Bildanov, and Vyacheslav Vikhrenko, Thermodynamic Properties of the System with Competing Interactions on a Triangular Lattice. Proceedings of the 2017 IEEE 7th International Conference on Nanomaterials: Applications & Properties (NAP-2017). Part 3. Paper 03NNSA31 (5p).
O. V. Patsahan, T. M. Patsahan, and M. F. Holovko Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: collective variables-based approach, arXiv:1708.08397.
Hadrian Montes-Campos, Jose Manuel Otero-Mato, Trinidad Mendez-Morales, Oscar Cabeza, Luis J. Gallego, Alina Ciach, and Luis M. Varela, Two-dimensional pattern formation in ionic liquids confined between graphene walls, Phys. Chem. Chem. Phys. 19 24505-24512 (2017) (the manuscript can be downloaded here).
Konrad Breitsprecher, Manuel Abele, Svyatoslav Kondrat, and Christian Holm, The effect of finite pore length on ion structure and charging, J. Chem. Phys. 146 104708 (2017)(the manuscript can be downloaded here).
