2017, Kargarfard, Neda, Diedrich, Norman, Rupp, Harald, Döhler, Diana, Binder, Wolfgang H.

Investigation of the curing kinetics of crosslinking reactions and the development of optimized catalyst systems is of importance for the preparation of self-healing nanocomposites, able to significantly extend their service lifetimes. Here we study different modified low molecular weight multivalent azides for a capsule-based self-healing approach, where self-healing is mediated by graphene-supported copper-nanoparticles, able to trigger “click”-based crosslinking of trivalent azides and alkynes. When monitoring the reaction kinetics of the curing reaction via reactive dynamic scanning calorimetry (DSC), it was found that the “click-crosslinking” reactivity decreased with increasing chain length of the according azide. Additionally, we could show a remarkable “click” reactivity already at 0 °C, highlighting the potential of click-based self-healing approaches. Furthermore, we varied the reaction temperature during the preparation of our tailor-made graphene-based copper(I) catalyst to further optimize its catalytic activity. With the most active catalyst prepared at 700 °C and the optimized set-up of reactants on hand, we prepared capsule-based self-healing epoxy nanocomposites.

2014, Akbarzadeh, Johanna, Puchegger, Stephan, Stojanovic, Anja, Kirchner, Helmut O.K., Binder, Wolfgang H., Bernstorff, Sigrid, Zioupos, Peter, Peterlik, Herwig

Strain (stress-free) relaxation in mechanically prestrained bone has a time constant of 75 s. It occurs by a reorganization of the proteoglycan-glycoprotein matrix between collagen fibers, which requires ionic interactions. Dissolving and relinking the ionic bonds is thus an important tool of nature to enable plastic deformation and to develop self-healing tissues. A way to transfer this approach to technical materials is the attachment of ionic end groups to polymeric chains. In these classes of materials, the so-called polymeric ionic liquids, structural recovery of thermally disorganized material is observed. A time constant between minutes and a week could be achieved, also by ionic rearrangement. The same mechanism, rearrangement of ionic bonds, can lead to vastly different relaxation times when the ionic interaction is varied by exchange of the cationic end groups or the anions.

2016, Appiah, Clement, Siefermann, Katrin R., Jorewitz, Marcel, Barqawi, Haitham, Binder, Wolfgang H.

A novel and efficient strategy in obtaining series of mono- and bi-armed azobenzene-containing poly(ε-caprolactone)s is described, starting from a commercially available azobenzene dye via azide/alkyne-“click”-reactions. The attachment of alkyne-telechelic poly(ε-caprolactone)s (1 kDa and 3 kDa), followed by chromatographic separation, allowed the attachment of either one or two PCl-chains to either side of the azobenzene-dye. The resulting mono- and bi-armed photo-switchable polymers are fully characterized by 2D-NMR techniques and show a high thermal stability. Additionally liquid chromatography at critical conditions (LCCC) coupled to ESI-TOF allowed us to prove the presence of either one or two polymer chains affixed onto the central azobenzene dye.