14 research outputs found
Polymer brush collapse under shear flow
Shear responsive surfaces offer potential advances in a number of
applications. Surface functionalisation using polymer brushes is one route to
such properties, particularly in the case of entangled polymers. We report on
neutron reflectometry measurements of polymer brushes in entangled polymer
solutions performed under controlled shear, as well as coarse-grained computer
simulations corresponding to these interfaces. Here we show a reversible and
reproducible collapse of the brushes, increasing with the shear rate. Using two
brushes of greatly different chain lengths and grafting densities, we
demonstrate that the dynamics responsible for the structural change of the
brush are governed by the free chains in solution rather than the brush itself,
within the range of parameters examined. The phenomenon of the brush collapse
could find applications in the tailoring of nanosensors, and as a way to
dynamically control surface friction and adhesion
Opportunities and challenges of surface scattering at next generation neutron sources
Complex fluids and soft matter are ubiquitously found in the world and all contacts in life are made over surfaces. To describe the mechanical behavior of such substances, rheological methods are used. Flow instabilities are a big challenge in rheology since they will be reflected in the macroscopic variables probed, like e. g. the viscosity. Many such discontinuities may actually originate at the surface. Investigating the properties of liquids in contact with the surface under mechanical load is the main course of the thesis. Neutron reflectometry and GISANS are perfect tools in this context to access the solid liquid interfaces, since they can penetrate many engineering materials and show a comparably large scattering potential at deuterated samples. In this thesis shear was applied on a model solution and neutron scattering techniques were used to investigate the structure under load. The focus was set on the development of the measurement methods themselves to enable new scientific insights in the future. First, by stroboscopic measurements the flux limitations are overcome for oscillatory rheology. By reintegration in the post processing it is shown that kinetic measurements with neutrons are possible with a time resolution below one millisecond. Second, the transformation of grazing incidence data from the laboratory system into q-space is strongly non-linear resulting in a need for re-binning. In this thesis a universal tool has been developed for this purpose. Finally, there is an ongoing discussion on depth sensitive neutron scattering experiments from solid-liquid boundaries. By using emission densities we show that such experiments face severe limitations due to the low absorption cross section of the neutron
Opportunities and challenges of surface scattering at next generation neutron sources
Complex fluids and soft matter are ubiquitously found in the world and all contacts in life are made over surfaces. To describe the mechanical behavior of such substances, rheological methods are used. Flow instabilities are a big challenge in rheology since they will be reflected in the macroscopic variables probed, like e. g. the viscosity. Many such discontinuities may actually originate at the surface. Investigating the properties of liquids in contact with the surface under mechanical load is the main course of the thesis. Neutron reflectometry and GISANS are perfect tools in this context to access the solid liquid interfaces, since they can penetrate many engineering materials and show a comparably large scattering potential at deuterated samples. In this thesis shear was applied on a model solution and neutron scattering techniques were used to investigate the structure under load. The focus was set on the development of the measurement methods themselves to enable new scientific insights in the future. First, by stroboscopic measurements the flux limitations are overcome for oscillatory rheology. By reintegration in the post processing it is shown that kinetic measurements with neutrons are possible with a time resolution below one millisecond. Second, the transformation of grazing incidence data from the laboratory system into q-space is strongly non-linear resulting in a need for re-binning. In this thesis a universal tool has been developed for this purpose. Finally, there is an ongoing discussion on depth sensitive neutron scattering experiments from solid-liquid boundaries. By using emission densities we show that such experiments face severe limitations due to the low absorption cross section of the neutron
Probing the dynamics of high-viscosity entangled polymers under shear using Neutron Spin Echo spectroscopy
Neutron Spin Echo spectroscopy provides unique insight into molecular and submolecular dynamics as well as intra-and inter-molecular interactions in soft matter. These dynamics may change drastically under shear flow. In particular in polymer physics a stress plateau is observed, which might be explained by an entanglement-disentanglement transition. However, such a transition is difficult to identify directly by experiments. Neutron Spin Echo has been proven to provide information about entanglement length and degree by probing the local dynamics of the polymer chains. Combining shear experiments and neutron spin echo is challenging since, first the beam polarisation has to be preserved during scattering and second, Doppler scattered neutrons may cause inelastic scattering. In this paper we present a new shear device adapted for these needs. We demonstrate that a high beam polarisation can be preserved and present first data on an entangled polymer solution under shear. To complement the experiments on the dynamics we present novel SANS data revealing shear-induced conformational changes in highly entangled polymers
The viscoelastic signature underpinning polymer deformation under shear flow
Entangled polymers are deformed by a strong shear flow. The shape of the polymer, called the form factor, is measured by small angle neutron scattering. However, the real-space molecular structure is not directly available from the reciprocal-space data, due to the phase problem. Instead, the data has to be fitted with a theoretical model of the molecule. We approximate the unknown structure using piecewise straight segments, from which we derive an analytical form factor. We fit it to our data on a semi-dilute entangled polystyrene solution under in situ shear flow. The character of the deformation is shown to lie between that of a single ideal chain (viscous) and a cross-linked network (elastic rubber). Furthermore, we use the fitted structure to estimate the mechanical stress, and find a fairly good agreement with rheology literature
Dissolution mechanism of supported phospholipid bilayer in the presence of amphiphilic drug investigated by neutron reflectometry and quartz crystal microbalance with dissipation monitoring
The influence and interaction of the ionizable amphiphilic drug amitriptyline hydrochloride (AMT) on a 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) phospholipid bilayer supported on a silica surface have been investigated using a combination of neutron reflectometry and quartz crystal microbalance with dissipation monitoring. Adding AMT solutions with concentrations 3, 12, and 50 mM leaves the lipid bilayer mainly intact and we observe most of the AMT molecules attached to the head-group region of the outer bilayer leaflet. Virtually no AMT penetrates into the hydrophilic head-group region of the inner leaflet close to the silica surface. By adding 200 mM AMT solution, the lipid bilayer dissolved entirely, indicating a threshold concentration for the solubilization of the bilayer by AMT. The observed threshold concentration is consistent with the observation that various bilayer structures abruptly transform into mixed AMT-DOPC micelles beyond a certain AMT-DOPC composition. Based on our experimental observations, we suggest that the penetration of drug into the phospholipid bilayer, and subsequent solubilization of the membrane, follows a two-step mechanism with the outer leaflet being removed prior to the inner leaflet
Core code of the software Överlåtaren
The core code of the software Överlåtaren, as is presented in the article PO5077 ''Överlåtaren' a fast way to transfer and orthogonalize 2D offspecular reflectivity data' in the Journal of Applied Crystallograph
Direct measurement of topological interactions in polymers under shear using neutron spin echo spectroscopy
We present in-situ neutron spin echo measurements on an entangled polydimethylsiloxane melt under shear and demonstrate the ability to monitor nano-scale dynamics in flowing liquids. We report no changes in the topological interactions of the chains for shear rates approaching the inverse longest relaxation time. Further experiments following along this line will allow to systematically test the predictions of theories, like e.g. convective constraint release