Martin Kraska

Pressure induced structure formation in Langmuir monolayers of amphiphilic metallocene diblock copolymers.

We present in situ structural investigations of a metal-containing diblock copolymer on a water surface. Monolayers of poly(vinylferrocene-b-(2-vinylpyridine)) (PVFc-b-P2VP) block copolymers are studied in a wide range of compositions by varying molar masses of P2VP with two different molecular weights of PVFc. We focus on the role of the respective block partners, PVFc and P2VP, when compressing the layer on the water surface. Compression isotherms are presented and interpreted in terms of the classical gaseous, expanded, and condensed phases. We calculate isothermal compressibilities, which reveal a minimum value independent of the molar masses of the respective block partners. We find the isotherms to be dominated by P2VP while PVFc barely contribute to the compression behavior due to its rather compact coil structure. We consider the diblock copolymer monolayers as a two-dimensional model system, which is reflected by two-dimensional scaling behavior in the semi dilute and condensed regime. By X-ray reflectometry (XR), we monitor in situ the monolayer structure change with increasing surface pressure Π and observe the PVFc-b-P2VP separation at high Π.

AOT microemulsions: droplet size and clustering in the temperature range between the supercooled state and the upper phase boundary

The main focus of this work is the investigation of the mechanism of droplet aggregation and the droplet structure of water–AOT (sodium bis(2-ethyl hexyl) sulfosuccinate)–decane microemulsions between the supercooled state and the upper phase boundary by means of SAXS. We study the temperature dependent droplet structure and size in detail at compositions of droplet volume fractions ϕ = 0.1–0.4 and water/AOT molar ratios of ω = 5–40. We found a change in droplet size at varying temperatures and explain our results by the change of the effective droplet surface covered by an AOT molecule (between the two phase boundaries) and by macro-phase separated water ice below a certain supercooling temperature. We monitor the continuous change of droplet interaction by means of a phenomenological structure factor combining hard sphere interactions with a Lorentzian function accounting for droplet density fluctuations in the system. We analyse the droplet aggregates in dependency on ϕ and ω leading to a better understanding of droplet aggregation with increasing temperature.

Concentration induced ordering of microemulsion droplets in bulk and near the liquid–air interface

The structure of the air interface of water–AOT (sodium bis(2-ethyl hexyl) sulfosuccinate)–decane microemulsions in the droplet phase with ω = 20, 30, 40 is studied in a range of compositions with droplet volume fractions of ϕ = 0.2 to 0.7. A combination of small angle X-ray scattering (SAXS) and X-ray reflectometry (XR) reveals a detailed image of the morphology in the bulk and at the microemulsion–air interface. The structure of the volume is described in terms of effective structure factors to obtain the bulk droplet structure and correlations. With increasing droplet density ϕ the droplets remain unchanged in their size and show an increase in the local order. The reflectivity behaviour of the samples can be consistently explained by bulk small angle scattering and specular reflectivity at the surface. The microemulsion–air interface consists of droplets with the same ϕ-dependent local order as in the bulk, e.g. we found a droplet volume fraction induced ordering of droplets.

Interaction between a water-in-oil microemulsion and a linear-dendritic poly(propylene oxide)–polyglycerol block copolymer

We present small angle scattering and dielectric spectroscopy results on the influence of an amphiphilic diblock copolymer on the structure and dynamics of a microemulsion. We use a water-in-oil (w/o) droplet microemulsion based on the anionic surfactant AOT (sodium bis(2-ethylhexyl) sulfosuccinate), that forms spherical water droplets coated by a monolayer of AOT dispersed in the continuous oil matrix. The studied polymer consists of a hydrophobic poly(propylene oxide) (PPO) block and a hydrophilic hyperbranched polyglycerol with 74 glycerol units (NG74). Combining small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS) we find that the droplet structure is preserved upon addition of PPO-NG74 while the interaction distance between droplets increases with increasing polymer content. From SANS we deduce that the NG74 block is located inside the droplets while the PPO extends into the oil matrix. By measuring the dc-conductivity as a function of temperature we study the dynamic percolation of the microemulsion. While the static structure of the droplet phase remains unchanged, both percolation temperature and phase separation temperature increase linearly with increasing polymer concentration. We explain this finding by a stiffening of the AOT layer induced by the polymer. By means of dielectric spectroscopy we observe two relaxations. The slower one can be related to a polarization at the interface of the water core and the AOT shell (core relaxation) and the faster one is due to the ions in the AOT-shell (cluster relaxation). Polymer addition is found to have a significant influence only on the core relaxation. We apply the cluster relaxation model to estimate the cluster size evolution with increasing polymer concentration.

On the supramacromolecular structure of core–shell amphiphilic macromolecules derived from hyperbranched polyethyleneimine

The supramacromolecular structure of core-shell amphiphilic macromolecules (CAMs) with hyperbranched polyethyleneimine (HPEI) cores and fatty acid chain shells (HPEI-Cn) for different chain lengths was investigated both, in colloidal suspension, solid phase and at the air-water interface using Small Angle X-ray Scattering (SAXS), Wide Angle X-ray Scattering (WAXS), X-ray Reflectometry (XRR) and Langmuir isotherms. At low temperatures colloidal toluene suspensions of the HPEI-Cn polymers form, as evidenced by peaks arising in the structure factor of the system showing mean particle-to-particle distances correlated with the length of the aliphatic chains forming the shells of HPEI-Cn unimicelles. The CAM sizes as found from the SAXS experiments also display a clear dependence on shell thickness suggesting that the aliphatic chains adopt a brush-like configuration. After solvent extraction, HPEI-Cn adopts ordered structures with hexagonal packing of the aliphatic chains. Submitted to lateral pressure Π at the air-water interface, HPEI-Cn undergoes a disorder-order transition with increasing transition pressure for increasing chain lengths. The CAMs show different behaviors in-plane and out-of-plane. While out-of-plane the aliphatic chains behave as a brush remaining almost fully unfolded, whereas parallel to the air-water interface the chains fold down in a mushroom way with increasing lateral pressure Π.

Polymer Chain Conformation on Deuterated Polystyrene Nanoparticles Investigated by SANS

We previously reported that grafted polystyrene (PS) chains on silica nanoparticles at a low grafting density show similar conformations to free PS chains in the same solvent, THF (diameter ˜50 nm, Colloid.poly.Sci. (2013), 291, 9, 2087–2099). As an extension of our previous study we choose an organic nanoparticle (deuterated polystyrene, dPS) instead of inorganic nanoparticle to see the impact of the substrate material on chain conformation. Additionally, a wider range of molecular weights were prepared to investigate the conformation feature of grafted PS chains more in detail. Small angle neutron scattering (SANS) experiments were performed to characterize PS grafted dPS particles in good solvent condition, with deuterated toluene and deuterated THF as solvent. To get insight into the conformation of the grafted PS layer we apply a scaling law describing the dimension of free PS polymer in good solvent condition to the obtained thickness of the grafted PS layer. We find an overall agreement with the scaling law where the thickness of the grafted PS layer is slightly larger than 2Rg of the free polymer chains in the respective solvent giving hint for semi dilute polymer brush (SDPB) situation.

Aggregate Structure and Dynamic Percolation in Microemulsions

This contribution deals with a special class of soft matter systems called microemulsions. They are mixtures of oil and water stabilized with a surfactant. The stabilisation is achieved through the reduction of interfacial tension by the amphiphilic surfactant. They thus consist of oil and water phases separated by a surfactant layer. The nanoscopic structure of these phases, in particular that of spherical nano droplets, is analysed in this chapter. The impact of temperature and mixing ratio of the constituents is shown. The fascinating phenomenon of dynamic droplet percolation and aggregation near a temperature induced phase separation are discussed. Microemulsions provide an excellent model system for the investigation of confinement effects on molecules. Conversely these guest molecules modify structural and dynamical properties of the microemulsion. This may even lead to the formation of transient networks with short time gel-like and long time self-diffusion dynamics of droplets.