Surface rheology of block-copolymer stabilized interfaces: a combined computational & experimental study. SNF project 200021_156106 at www.complexfluids.ethz.ch/snf15
Graphene is recognized as an emerging 2D nanomaterial for many applications. Assembly of graphene sheets into 3D structures is an attractive way to enable their macroscopic applications and to preserve the exceptional mechanical and physical properties of their constituents. In this study, we develop a coarse-grained (CG) model for 3D graphene foams (GFs) based on the CG model for a 2D graphene sheet by Ruiz et al (2015 Carbon 82 103-15). We find that the size of graphene sheets plays an important role in both the structural and mechanical properties of 3D GFs. When their size is smaller than 10 nm, the graphene sheets can easily stack together under the influence of van der Waals interactions (vdW). These stacks behave like building blocks and are tightly packed together within 3D GFs, leading to high density, small pore radii, and a large Young's modulus. However, if the sheet sizes exceed 10 nm, they are staggered together with a significant amount of deformation (bending). Therefore, the density of 3D GFs has been dramatically reduced due to the loosely packed graphene sheets, accompanied by large pore radii and a small Young's modulus. Under uniaxial compression, rubber-like stress-strain curves are observed for all 3D GFs. This material characteristic is dominated by the vdW interactions between different graphene layers and slightly affected by the out-of-plane deformation of the graphene sheets. We find a simple scaling law E similar to rho(4.2) between the density rho and Young's modulus E for a model of 3D GFs. The simulation results reveal structure-property relations of 3D GFs, which can be applied to guide the design of 3D graphene assemblies with exceptional properties. Kroger, Martin/C-1946-2008; Shen, Zhiqiang/O-5073-2019; Li, Ying/B-9378-2008 Kroger, Martin/0000-0003-1402-6714; Shen, Zhiqiang/0000-0003-0804-2478; Li, Ying/0000-0002-1487-3350 Department of Mechanical Engineering at the University of Connecticut; GE Fellowship for Innovation; National Science Foundation [ACI-1053575]; Swiss National Science Foundation [200021_156106] Z S, H Y, and Y L are grateful for the support from the Department of Mechanical Engineering at the University of Connecticut. Z S and H Y would like to acknowledge the partial financial support from the GE Fellowship for Innovation. This research benefited in part from the computational resources and staff contributions provided by the Booth Engineering Center for Advanced Technology (BECAT) at the University of Connecticut. Part of this work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation under grant number ACI-1053575. M K was supported by the Swiss National Science Foundation through grant 200021_156106. [hide]
Principal Investigators
Leonard Sagis (PL)
Polymer Physics, ETH Zurich, Switzerland ►
Wageningen University, Netherlands ►
Patrick Ilg (PL)
Polymer Physics, ETH Zurich, Switzerland ►
University of Reading, United Kingdom ►
Peter Fischer (Co-PI)
Inst. Food, nutrition and health, ETH Zurich, Switzerland ►
Martin Kröger (PI)
Polymer Physics, ETH Zurich, Switzerland ►
Secretary
Patricia Horn
Polymer Physics, ETH Zurich, Switzerland ►
Involved Students
Ahmad Moghimikheirabadi
Polymer Physics, ETH Zurich, Switzerland ►
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Selected conferences (co-)organized by project members
IWNET 2015
05 Jul - 10 Jul 2015, 7th International workshop on nonequilibrium thermodynamics (IWNET 2015), Hilvarenbeek, The Netherlands ►
learn more ► About this project
Complex fluid-fluid interfaces are interfaces in which the adsorbed species self-assemble into complex microstructures. Such interfaces are ubiquitous in nature, industrial processes, and consumer products, and can be found in living cells, nano- and microcapsules, vesicles, food emulsions, or foam. Compared to simple liquid-like interfaces (stabilized by low molecular weight surfactants), complex interfaces display significant viscoelasticity, with high values for their surface shear and dilatational moduli. Their stress-deformation behavior dominates the macroscopic dynamics of multiphase materials that contain such interfaces, and when this occurs those materials can be referred to as Interface-Dominated Materials (IDMs).Complex interfaces can be formed by a wide range of surface active components, such as proteins, colloidal particles, polymers, lipids, or mixtures of these components. In this proposal we will focus on complex interfaces stabilized by amphiphilic multi-block copolymers. These polymers consist of alternating blocks of a hydrophilic repeating unit A, and a hydrophobic repeating unit B. Amphiphilic copolymers can form interfaces with exceptional mechanical properties. This makes them ideal candidates for application in highly stable emulsions, or encapsulation systems with high mechanical stability, for application in food and pharmaceutical products.
Amphiphilic copolymers may form 2d gels, 2d (soft) glass phases, 2d (liquid) crystalline phases, or even 2d metastable emulsions (phase-separated mixtures of immiscible copolymers) after adsorption. The type of structure formed depends on surface concentration, and length, distribution, rigidity, and hydrophobicity of the sub-blocks of the copolymer. The response of polymer stabilized fluid-fluid interfaces to deformations or gradients in temperature is often highly nonlinear. The nonlinearity in their response to perturbations is a result of changes in this interfacial microstructure, induced by the applied gradients. The effect of deformations on interfacial microstructure, and the effect of these changes on macroscopic dynamics of interface-dominated materials is still poorly understood. A more fundamental understanding of the nonlinear response of polymer interfaces, is essential for a targeted design of high-end polymer stabilized IDMs, such as encapsulation systems with environmental triggers, nanoparticles with structured interfaces, or foam and emulsions with extreme stability. In view of the widespread occurrence of IDMs, the study of dynamic mechanical properties of these interfaces is highly relevant for many disciplines, such as colloid and interface science, physical chemistry, polymer physics, pharmaceutical science, food science, coating technology, or soft matter physics.
The aim of this project is to characterize the microstructure and mechanical properties of interfaces stabilized by multi-block copolymers, using a multiscale multidisciplinary approach, which integrates state of the art computational methods with surface rheological experiments, and experimental interfacial structure evaluation. The computational modeling will be done using Monte Carlo (MC) and Molecular Dynamics (MD) simulations. We will measure both shear and dilatational surface properties, and the microstructure will be evaluated using various forms of microscopy (AFM, TEM, SEM), and neutron and X-ray reflectivity measurements. We will determine the mechanical properties and interfacial structure as a function of surface polymer concentration, chemical structure of the polymers (variation of number, size, and distribution of blocks), and degree of hydrophobicity and rigidity of the sub-blocks. A detailed insight in the dynamic behavior of copolymer interfaces will provide new insight in the macroscopic dynamic behavior of polymer stabilized interface-dominated materials (emulsions, foam, encapsulation systems, nanoparticles), and will allow a more targeted design of these systems with tailor made properties, tuned for specific industrial applications.
29 April 2024 mk