Fourier-transform rheology on anionically synthesised polymer melts and solutions of various topology

Aim of this thesis was to further extend the applicability of the Fourier-transform (FT) rheology technique especially for non-linear mechanical characterisation of polymeric materials on the one hand and to investigated the influence of the degree of branching on the linear and non-linear relaxation behaviour of polymeric materials on the other hand. The latter was achieved by employing in particular FT-rheology and other rheological techniques to variously branched polymer melts and solutions. For these purposes, narrowly distributed linear and star-shaped polystyrene and polybutadiene homo-polymers with varying molecular weights were anionically synthesised using both high-vacuum and inert atmosphere techniques. Furthermore, differently entangled solutions of linear and star-shaped polystyrenes in di-sec-octyl phthalate (DOP) were prepared. The several linear polystyrene solutions were measured under large amplitude oscillatory shear (LAOS) conditions and the non-linear torque response was analysed in the Fourier space. Experimental results were compared with numerical predictions performed by Dr. B. Debbaut using a multi-mode differential viscoelastic fluid model obeying the Giesekus constitutive equation. Apart from the analysis of the relative intensities of the harmonics, a detailed examination of the phase information content was developed. Further on, FT-rheology allowed to distinguish polystyrene melts and solutions due to their different topologies where other rheological measurements failed. Significant differences occurred under LAOS conditions as particularly reflected in the phase difference of the third harmonic, Ħ3, which could be related to shear thinning and shear thickening behaviour.

Rheology and Fourier-transform rheology on water-based systems

The influence of shear fields on water-based systems was investigated within this thesis. The non-linear rheological behaviour of spherical and rod-like particles was examined with Fourier-Transform rheology under LAOS conditions. As a model system for spherical particles two different kinds of polystyrene dispersions, with a solid content higher than 0.3 each, were synthesised within this work. Due to the differences in polydispersity and Debye-length, differences were also found in the rheology. In the FT-rheology both kinds of dispersions showed a similar rise in the intensities of the magnitudes of the odd higher harmonics, which were predicted by a model. The in some cases additionally appearing second harmonics were not predicted. A novel method to analyse the time domain signal was developed, that splits the time domain signal up in four characteristic functions. Those characteristic functions correspond to rheological phenomena. In some cases the intensities of the Fourier components can interfere negatively. FD-virus particles were used as a rod-like model system, which already shows a highly non-linear behaviour at concentrations below 1. % wt. Predictions for the dependence of the higher harmonics from the strain amplitude described the non-linear behaviour well at large, but no so good at small strain amplitudes. Additionally the trends of the rheological behaviour could be described by a theory for rod-like particles. An existing rheo-optical set-up was enhanced by reducing the background birefringence by a factor of 20 and by increasing the time resolution by a factor of 24. Additionally a combination of FT-rheology and rheo-optics was achieved. The influence of a constant shear field on the crystallisation process of zinc oxide in the presence of a polymer was examined. The crystallites showed a reduction in length by a factor of 2. The directed addition of polymers in combination with a defined shear field can be an easy way for a defined change of the form of crystallites.

Describing and explaining the foreign expansion of network managing electronic business companies (NM-EBCs)

This study deals with the internationalization behavior of a new and specific type of e-business company, namely the network managing e-business company (NM-EBC). The business model of such e-business companies is based on providing a platform and applications for users to connect and interact, on gathering and channeling the inputs provided by the users, and on organizing and managing the cross-relationships of the various participants. Examples are online communities, matching platforms, and portals. Since NM-EBCs internationalize by replicating their business model in a foreign market and by building up and managing a network of users, who provide input themselves and interact with each other, they have to convince users in foreign markets to join the network and hence to adopt their platform. We draw upon Rogers’ Diffusion of Innovations Theory and Network Theory to explain the internationalization behavior of NM-EBCs. These two theories originate from neighboring disciplines and have not yet been used to explain the internationalization of firms. We combine both theories and formulate hypotheses about which strategies NM-EBCs may choose to expand abroad. To test the applicability of our theory and to gain rich data about the internationalization behavior of these firms, we carried out multiple case studies with internationally active Germany-based NM-EBCs.