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

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

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

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

Depth resolved grazing incidence neutron scattering experiments from semi-infinite interfaces: a statistical analysis of the scattering contributions

Grazing incidence neutron scattering experiments offer surface sensitivity by reflecting from an interface at momentum transfers close to total external reflection. Under these conditions the penetration depth is strongly non-linear and may change by many orders of magnitude. This fact imposes severe challenges for depth resolved experiments, since the brilliance of neutron beams is relatively low in comparison to e.g. synchrotron radiation. In this article we use probability density functions to calculate the contribution of scattering at different distances from an interface to the intensities registered on the detector. Our method has the particular advantage that the depth sensitivity is directly extracted from the scattering pattern itself. Hence for perfectly known samples exact resolution functions can be calculated and visa versa. We show that any tails in the resolution function, e.g. Gaussian shaped, hinders depth resolved experiments. More importantly we provide means for a descriptive statistical analysis of detector images with respect to the scattering contributions and show that even for perfect resolution near surface scattering is hardly accessible