A mechanochromic donor-acceptor torsional spring

Mechanochromic polymers are intriguing materials that allow to sense force of specimens under load. Most mechanochromic systems rely on covalent bond scission and hence are two-state systems with optically distinct “on” and “off” states where correlating force with wavelength is usually not possible. Translating force of different magnitude with gradually different wavelength of absorption or emission would open up new possibilities to map and understand force distributions in polymeric materials. Here, we present a mechanochromic donor-acceptor (DA) torsional spring that undergoes force-induced planarization during uniaxial elongation leading to red-shifted absorption and emission spectra. The DA spring is based on ortho-substituted diketopyrrolopyrrole (o-DPP). Covalent incorporation of o-DPP into a rigid yet ductile polyphenylene matrix allows to transduce sufficiently large stress to the DA spring. The mechanically induced deflection from equilibrium geometry of the DA spring is theoretically predicted, in agreement with experiments, and is fully reversible upon stress release.

Shear and Extensional Rheology of Linear and Branched Polybutylene Succinate Blends

The molecular architecture and rheological behavior of linear and branched polybutylene succinate blends have been investigated using size-exclusion chromatography, small-amplitude oscillatory shear and extensional rheometry, in view of their processing using cast and blown extrusion. Dynamic viscoelastic properties indicate that a higher branched polybutylene succinate amount in the blend increases the relaxation time due to an increased long-chain branching degree. Branched polybutylene succinate exhibits pronounced strain hardening under uniaxial elongation, which is known to improve processability. Under extensional flow, the 50/50 wt % blend exhibits the same behavior as linear polybutylene succinate.

Advanced Constitutive Modeling of the Thixotropic Elasto-Visco-Plastic Behavior of Blood: Description of the Model and Rheological Predictions

This work focuses on the advanced modeling of the thixotropic nature of blood, coupled with an elasto-visco-plastic formulation by invoking a consistent and validated model for TEVP materials. The proposed model has been verified for the adequate description of the rheological behavior of suspensions, introducing a scalar variable that describes dynamically the level of internal microstructure of rouleaux at any instance, capturing accurately the aggregation and disaggregation mechanisms of the RBCs. Also, a non-linear fitting is adopted for the definition of the model’s parameters on limited available experimental data of steady and transient rheometric flows of blood samples. We present the predictability of the new model in various steady and transient rheometric flows, including startup shear, rectangular shear steps, shear cessation, triangular shear steps and LAOS tests. Our model provides predictions for the elasto-thixotropic mechanism in startup shear flows, demonstrating a non-monotonic relationship of the thixotropic index on the shear-rate. The intermittent shear step test reveals the dynamics of the structural reconstruction, which in turn is associated with the aggregation process. Moreover, our model offers robust predictions for less examined tests such as uniaxial elongation, in which normal stress was found to have considerable contribution. Apart from the integrated modeling of blood rheological complexity, our implementation is adequate for multi-dimensional simulations due to its tensorial formalism accomplished with a single time scale for the thixotropic effects, resulting in a low computational cost compared to other TEVP models.