In photopolymerization reactions, mostly multifunctional monomers are employed, as they ensure fast reaction times and good final mechanical properties of the cured materials. Drawing conclusions about the influence of the components and curing conditions on the mechanical properties of the subsequently formed insoluble networks is challenging. Therefore, an in situ observation of chemical and mechanical characteristics during the photopolymerization reaction is desired. By coupling of an infrared spectrometer with a photorheometer, a broad spectrum of different photopolymerizable formulations can be analyzed during the curing reaction. The rheological information (i.e., time to gelation, final modulus, shrinkage force) can be derived from a parallel plate rheometer equipped with a UV- and IR-translucent window (glass for NIR and CaF window for MIR). Chemical information (i.e., conversion at the gel point and final conversion) is gained by monitoring the decrease of the corresponding IR-peak for the reactive monomer unit (e.g., C═C double bond peak for (meth)acrylates, H-S thiol and C═C double bond peak in thiol-ene systems, C-O epoxy peak for epoxy resins). Depending on the relative concentration of reactive functional groups in the sample volume and the intensity of the IR signal, the conversion can be monitored in the near-infrared region (e.g., acrylate double bonds, epoxy groups) or the MIR region (e.g., thiol signal). Moreover, an integrated Peltier element and external heating hood enable the characterization of photopolymerization reactions at elevated temperatures, which also widens the window of application to resins that are waxy or solid at ambient conditions. By switching from water to heavy water, the chemical conversion during photopolymerization of hydrogel precursor formulations can also be examined. Moreover, this device could also represent an analytical tool for a variety of thermally and redox initiated systems.
A new experimental method for studying the mechano-optical rheology of polymeric liquids and soft matter materials is presented. The method is based on a combination of rotational rheology and a recently developed optical technique-shear-induced polarized light imaging (SIPLI). The method provides a unique opportunity to monitor a complete sample view during rheological measurements in plate-plate and cone-and-plate geometry. Applications of the method are presented including simultaneous SIPLI and the rheology of the oriented lamellar phase of block copolymers and liquid crystals as well as a study of the thermally induced reversible transformation of worm-like micelles to spherical micelles. In addition, a direct relation between the shish formation and the polymer melt viscosity upturn during flow-induced crystallization of semi-crystalline polymers is demonstrated. An application of SIPLI for quantitative birefringence measurements is also shown.
Stribeck curves have long been used for understanding the lubricating behaviour of oils and greases, and in the recent years for applications ranging from ball point inks to synovial fluids. In the current work, an attempt is made to show as to what one can read from Stribeck curves of food samples such as chocolate spread, sauce etc. Additionally, the effect of salivahuman and artificialon the frictional behaviour has also been studied. The tests were carried out on an MCR Tribometer with a ball-on-three-pin configuration. Polydimethylsiloxane and glass were used to simulate soft contact conditions that exist in the human mouth. Results from the tribological tests are plotted in the form of extended Stribeck curves, wherein, the friction coefficient is plotted as a function of rotational speed. Since the tribometer is capable of speeds as low as a few nanometres per second, it is also possible to observe the build-up of static friction and its transition into the kinetic regime of friction. Results indicate that certain aspects of the Stribeck curve can offer an insight into the correlation between the frictional behaviour of food to their sensory feel.
The typical interconnected bicontinuous percolation structure of a critical 50/50 wt % polybutadiene (PB)/polyisoprene (PI) mixture was characterized in detail by the structure function of a light scattering experiment and by statistical image processing of optical microscope images. The time development of the interdomain distance and the local radius of the curved interface in the late stage of the spinodal decomposition are obtained for the first time for the same system by both methods and are found to be in good agreement. PB/PI blends are systems with a lower critical solution temperature (LCST). The critical point was varied within a wide temperature range by changing the 1,2 content of the PB. For optical microscopy, the structure was fixed by photo-cross-linking and the optical contrast was achieved in a second step by selective staining of the PI phase by exposing the sample to iodine vapor.
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