Periodic Reporting for period 2 - nanoPaInt (Dynamics of dense nanosuspensions: a pathway to novel functional materials)
Reporting period: 2023-01-01 to 2025-10-31
Nanoparticles are used as additives to modify and control liquid properties and to stabilize foams and emulsions for possible application in the food, cosmetics and materials industries. They are the essential part of ink formulations for 2D and 3D printing and coatings, and very promising carriers for targeted drug delivery. Nanoparticles are incorporated into functional porous materials, designed for applications requiring extremely high surface area enabling high heat and mass transport and chemical reactions rates.
The aim of the nanoPaInt project is a comprehensive understanding and predictive modelling of the properties and dynamics of dense nanosuspensions, which are governed by strong nanoparticles interactions in liquid bulk and at interfaces. The gained knowledge is used to design novel functional smart liquids and solid nanomaterials.
The training aim of nanoPaInt network is to support the career development of young researchers both in academic and non-academic sectors and to train a new generation of creative, mobile, entrepreneurial and innovative early-stage researchers.
Work Package (WP) 1 focuses on the interactions between nanoparticles in liquid bulk and at fluid interfaces, as well as the dynamics of these interactions and their relation to the bulk and surface rheology of nanosuspensions.
WP 2 is focussed on investigation of dynamic interfacial flows which are important for manufacturing and application of functional nanomaterials. This includes the fast elongational flow in liquid bridge, flow of films and sessile drops induced by vibrations and fast spreading under influence of surfactants. In these flows the relation between the time scale of the flow and the time scale of nanoparticles dynamics, including the adsorption/desorption kinetics, plays an important role.
In WP 3, capillary nanosuspensions are being designed and fabricated with the forces between the nanoparticles responding to external stimuli, which allows programming the response of the suspensions to changes in environmental pH, temperature or salinity. Capillary suspensions can also be used as precursors for fabrication of porous ceramic materials.
WP 4 is devoted to development and optimization of routes for manufacturing of novel functional nanomaterials from dense nanosuspensions on the basis of knowledge gained in the previous WPs. We shall demonstrate the applicability of nano-suspensions with controlled properties for manufacturing of functional materials and parts at different scales and shapes: micron-sized supraparticles, printed electronic circuits, porous materials and objects manufactured using 3D-printing process. Their applications include catalysis, gas adsorption, filtration, liquids separation and drug delivery.
Conclusions:
The project delivered new theoretical, computational, and experimental tools for understanding and controlling nanoparticle interactions, interfacial dynamics, and particle laden microstructures. Numerical simulations enable prediction of colloidal interactions and gel evolution. Advanced experimental methods provided frequency dependent interfacial rheology and clarified nanoparticle adhesion mechanisms relevant to dry coated battery electrodes. Non isothermal models for nano suspensions were established and applied to several interfacial flow configurations. Stimuli responsive capillary (nano)suspensions with superior rheology were created and studied. A comprehensive computational and theoretical framework was developed to connect microstructure of capillary (nano)suspensions to rheological properties. New numerical approaches captured nanoparticle assembly during evaporation of nanosuspensions, guiding the fabrication of nanomaterials. Novel routes were developed to synthetize hybride Cu@Ag core@shell nanowires for conductive inks. New protocols were developed for manufacturing Janus supraparticles, porous photocatalytic foams, as well as sol gel–derived silica phosphate nanoparticles, enabling advanced functional materials and printable glass formulations.
The aim of the nanoPaInt project is a comprehensive understanding and predictive modelling of the properties and dynamics of dense nanosuspensions, which are governed by strong nanoparticles interactions in liquid bulk and at interfaces. The gained knowledge is used to design novel functional smart liquids and solid nanomaterials.
The training aim of nanoPaInt network is to support the career development of young researchers both in academic and non-academic sectors and to train a new generation of creative, mobile, entrepreneurial and innovative early-stage researchers.
Work Package (WP) 1 focuses on the interactions between nanoparticles in liquid bulk and at fluid interfaces, as well as the dynamics of these interactions and their relation to the bulk and surface rheology of nanosuspensions.
WP 2 is focussed on investigation of dynamic interfacial flows which are important for manufacturing and application of functional nanomaterials. This includes the fast elongational flow in liquid bridge, flow of films and sessile drops induced by vibrations and fast spreading under influence of surfactants. In these flows the relation between the time scale of the flow and the time scale of nanoparticles dynamics, including the adsorption/desorption kinetics, plays an important role.
In WP 3, capillary nanosuspensions are being designed and fabricated with the forces between the nanoparticles responding to external stimuli, which allows programming the response of the suspensions to changes in environmental pH, temperature or salinity. Capillary suspensions can also be used as precursors for fabrication of porous ceramic materials.
WP 4 is devoted to development and optimization of routes for manufacturing of novel functional nanomaterials from dense nanosuspensions on the basis of knowledge gained in the previous WPs. We shall demonstrate the applicability of nano-suspensions with controlled properties for manufacturing of functional materials and parts at different scales and shapes: micron-sized supraparticles, printed electronic circuits, porous materials and objects manufactured using 3D-printing process. Their applications include catalysis, gas adsorption, filtration, liquids separation and drug delivery.
Conclusions:
The project delivered new theoretical, computational, and experimental tools for understanding and controlling nanoparticle interactions, interfacial dynamics, and particle laden microstructures. Numerical simulations enable prediction of colloidal interactions and gel evolution. Advanced experimental methods provided frequency dependent interfacial rheology and clarified nanoparticle adhesion mechanisms relevant to dry coated battery electrodes. Non isothermal models for nano suspensions were established and applied to several interfacial flow configurations. Stimuli responsive capillary (nano)suspensions with superior rheology were created and studied. A comprehensive computational and theoretical framework was developed to connect microstructure of capillary (nano)suspensions to rheological properties. New numerical approaches captured nanoparticle assembly during evaporation of nanosuspensions, guiding the fabrication of nanomaterials. Novel routes were developed to synthetize hybride Cu@Ag core@shell nanowires for conductive inks. New protocols were developed for manufacturing Janus supraparticles, porous photocatalytic foams, as well as sol gel–derived silica phosphate nanoparticles, enabling advanced functional materials and printable glass formulations.
In WP 1, a modified Derjaguin approach for computation of interactions between nanoparticles was developed and validated against full Poisson–Boltzmann solutions, improving accuracy for a wide range of particle sizes and electrolyte conditions. Molecular and Brownian dynamics simulations were implemented to study gel formation and ageing in colloidal systems. Network topology metrics were extracted using graph-theory methods. These descriptors will inform constitutive models linking microstructure to macroscopic rheology.
High-frequency techniques such as electrocapillary waves and surface quasi-elastic light scattering were deployed alongside oscillating drop and Langmuir-trough methods. This multi-method approach delivered frequency-dependent viscoelastic profiles for nanoparticle-laden interfaces.
In the same work package, the mechanisms of nanoparticle adhesion and detachment to surfaces were explored, with a focus on the dry coating process and its application for manufacturing of batteries with improved performance and longevity.
In WP 2, a mathematical model for the description of the dynamics of a non-isothermal dense nano-suspension with a free interface has been developed. The model includes thermophoresis, adsorption and desorption of particles at the interface, and the dependence of properties on the particle concentration.
Interfacial flows of nanofluids were studied in the following configurations: (i) liquid bridge stretching, (ii) drop impact on a spherical target; (iii) vibrating sessile drops; (iv) spreading of drop in the presence of trisiloxane surfactants.
In WP 3, a combination of experiments and modelling approaches was directed to develop more stimuli-responsive and hence smarter capillary suspensions. Capillary suspensions with mixed nano‑ and microparticles were produced and showed superior rheological properties. The aqueous two-phase system PEG-dextran has been successfully used to produce completely water-based capillary suspensions. In addition, a comprehensive computational and theoretical framework was developed to connect microstructure to rheological properties. Computational modeling using ESPResSo with Lees-Edwards boundary conditions successfully reproduced experimental observations
In WP 4, a theoretical/numerical framework for describing formation of nanoparticle assemblies has been developed, in which the suspended particles are treated as a solute. The simulation were performed for evaporation of suspension sessile drops on super-hydrophobic and para-hydrophobic substrates.The evaporation of film of nanofluid from structured substrates was simulated.
Formation of smart supraparticles by evaporation of two coalescing drops on a superoleophobic substrates and was studied, and methods for manufacturing Janus and core@shell supraparticles have been tested.
Optimization of methods for syntheses of copper nanowires (NWs) and hybrid particles composed of Cu NWs coated by a silver layer (core@shell particles) was performed.
Protocols for obtaining porous materials in the form of solid foams were developed. Concentrated dispersions of photocatalytic titania nanopafrticles serve as a basis for the development of solid foams with satisfactory multiscale pore structure.
Silica-phosphate glass nanoparticles were formed through the sol-gel route, and silica-phosphate photo-printable ink for 3D printing of complex glassy objects was formulated.
High-frequency techniques such as electrocapillary waves and surface quasi-elastic light scattering were deployed alongside oscillating drop and Langmuir-trough methods. This multi-method approach delivered frequency-dependent viscoelastic profiles for nanoparticle-laden interfaces.
In the same work package, the mechanisms of nanoparticle adhesion and detachment to surfaces were explored, with a focus on the dry coating process and its application for manufacturing of batteries with improved performance and longevity.
In WP 2, a mathematical model for the description of the dynamics of a non-isothermal dense nano-suspension with a free interface has been developed. The model includes thermophoresis, adsorption and desorption of particles at the interface, and the dependence of properties on the particle concentration.
Interfacial flows of nanofluids were studied in the following configurations: (i) liquid bridge stretching, (ii) drop impact on a spherical target; (iii) vibrating sessile drops; (iv) spreading of drop in the presence of trisiloxane surfactants.
In WP 3, a combination of experiments and modelling approaches was directed to develop more stimuli-responsive and hence smarter capillary suspensions. Capillary suspensions with mixed nano‑ and microparticles were produced and showed superior rheological properties. The aqueous two-phase system PEG-dextran has been successfully used to produce completely water-based capillary suspensions. In addition, a comprehensive computational and theoretical framework was developed to connect microstructure to rheological properties. Computational modeling using ESPResSo with Lees-Edwards boundary conditions successfully reproduced experimental observations
In WP 4, a theoretical/numerical framework for describing formation of nanoparticle assemblies has been developed, in which the suspended particles are treated as a solute. The simulation were performed for evaporation of suspension sessile drops on super-hydrophobic and para-hydrophobic substrates.The evaporation of film of nanofluid from structured substrates was simulated.
Formation of smart supraparticles by evaporation of two coalescing drops on a superoleophobic substrates and was studied, and methods for manufacturing Janus and core@shell supraparticles have been tested.
Optimization of methods for syntheses of copper nanowires (NWs) and hybrid particles composed of Cu NWs coated by a silver layer (core@shell particles) was performed.
Protocols for obtaining porous materials in the form of solid foams were developed. Concentrated dispersions of photocatalytic titania nanopafrticles serve as a basis for the development of solid foams with satisfactory multiscale pore structure.
Silica-phosphate glass nanoparticles were formed through the sol-gel route, and silica-phosphate photo-printable ink for 3D printing of complex glassy objects was formulated.
The results obtained during the reporting period are novel, and the obtained results met the stated objectives. The developed mathematical/numerical models and experimental diagnostic tools are expected to have an important scientific impact in the area. The development of novel materials and methods of fabrication of functional objects are expected to have socio-economic impact. For example, the application of the dry coating process for manufacturing of batteries with improved performance and longevity contributes to energy storage technology and is expected to have a significant socio-economic impact.