Interfaces differ from bulk materials in many ways, one particular aspect is that they are compressible. Changing the area per molecule or per particle changes the thermodynamic state variables such as surface pressure. Yet, when compressing to high surface pressures, dense packing of the interfacial species induces phase transitions, with highly structured phases, which can display elastic or strongly viscoelastic behaviour. When these are deformed, in addition to the changes in the surface pressure, extra and deviatoric stresses can be induced. The traditional tool to study the phase behaviour of monolayers is a rectangular Langmuir-Pockels trough, but as both the area and shape of the interface are changed upon compression, the interfacial-strain field in this instrument is mixed with a priori unknown amounts of dilatational and shear deformations, making it difficult to separate the rheological and equilibrium thermodynamic effects. In the present work, the design of a radial trough is described, in which the deformation field is simple, purely dilation or compression. The possibility to now independently measure the compressional properties of different strains and the development of an appropriate finite strain constitutive model for elastic interfaces make it possible to interrogate the underlying constitutive behaviour. This is shown here for a strongly elastic, soft glassy polymer monolayer during its initial compression but is easily generalised to many viscoelastic soft matter interfaces.
In the present work a polymeric transient viscoelastic network is used as a model system to investigate several fundamentals of interfacial viscoelasticity and non-linear behavior, in simple shear, compression and for simple mixed deformations. A supramolecular polymer bilayer, characterized by long but finite relaxation times, is created at the water-air interface using a layer-by-layer assembly method. The possibility of studying the individual layers starting from an unstrained reference state enabled the independent quantification of the equilibrium thermodynamic properties, and the viscoelastic response of the bilayer could be studied separately for shear and compressional deformations. Time-and frequency-dependent material functions of the layer were determined in simple shear and uniform compression. Moreover, a quasi linear neo-Hookean model for elastic interfaces was adapted to describe step strain experiments on a viscoelastic system by allowing the material properties to be time-dependent. The use of this model made it possible to calculate the response of the system to step deformations. Within the linear response regime, both stress-strain proportionality and the superposition principle were investigated. Furthermore, the onset of non-linear behavior of the extra stresses was characterized in shear and for the first time in pure compression. We conclude by investigating the multilayer system in a rising bubble setup and show that the neo-Hookean model is able to predict the extra and deviatoric surface stresses well, up to moderate deformations.
The thermodynamic and rheological properties of densely packed dendronized polymers (DPs) at water–air interfaces were studied here for first- and fourth-generation DPs (PG1, PG4) with both small (P n ≈ 50) and large (P n ≈ 500) backbone degrees of polymerization. The excellent control over the structural characteristics of these polymers enabled us to investigate how the interfacial properties change as we go from thin, flexible macromolecules toward thicker molecular objects that display colloidal features. The effects of the dendron generation, affecting the persistence length, as well as the degree of polymerization and surface pressure on the formation of DP layers at the water–air interface were studied. Surface pressure measurements and interfacial rheology suggest the existence of significant attractive interactions between the molecules of the higher generation DPs. While all DPs featured reproducible Π–A diagrams, successive compression–expansion cycles and surface pressure relaxation experiments revealed differences in the stability of the formed films, which are consistent with the variations in shape persistence and interactions between the studied DPs. Atomic force microscopy after Langmuir–Blodgett transfer of the films displayed a nanostructuring that can be attributed to the increase in attractive forces with increasing polymer generation and anisotropy. The importance of such structures on the surface properties was probed by interfacial shear rheology, which validated the existence of strong albeit brittle structures for fourth-generation DPs. Ultimately, we demonstrate how in particular rod-like DPs can be used as robust foam stabilizers.
Microcapsules made of synthetic polymers are used for the release of cargo in agriculture, food, and cosmetics but are often difficult to be degraded in the environment. To diminish the environmental impact of microcapsules, we use the biofilm-forming ability of bacteria to grow cellulose-based biodegradable microcapsules. The present work focuses on the design and optimization of self-grown bacterial cellulose capsules. In contrast to their conventionally attributed pathogenic role, bacteria and their self-secreted biofilms represent a multifunctional class of biomaterials. The bacterial strain used in this work, Gluconacetobacter xylinus, is able to survive and proliferate in various environmental conditions by forming biofilms as part of its lifecycle. Cellulose is one of the main components present in these self-secreted protective layers and is known for its outstanding mechanical properties. Provided enough nutrients and oxygen, these bacteria and the produced cellulose are able to self-assemble at the interface of any given three-dimensional template and could be used as a novel stabilization concept for water-in-oil emulsions. Using a microfluidic setup for controlled emulsification, we demonstrate that bacterial cellulose capsules can be produced with tunable size and monodispersity. Furthermore, we show that successful droplet stabilization and bacterial cellulose formation are functions of the bacteria concentration, droplet size, and surfactant type. The obtained results represent the first milestone in the production of self-assembled biodegradable cellulose capsules to be used in a vast range of applications such as flavor, fragrance, agrochemicals, nutrients, and drug encapsulation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.