Ulrich Nöchel

Reversible Bidirectional Shape‐Memory Polymers

Free-standing copolymer network samples with two types of crystallizable domains are capable of a fully reversible bidirectional shape-memory effect. One set of crystallizable domains determines the shape-shifting geometry while the other provides the thermally controlled actuation capability.

Influence of Tyrosine-Derived Moieties and Drying Conditions on the Formation of Helices in Gelatin

The single and triple helical organization of protein chains strongly influences the mechanical properties of gelatin-based materials. A chemical method for obtaining different degrees of helical organization in gelatin is covalent functionalization, while a physical method for achieving the same goal is the variation of the drying conditions of gelatin solutions. Here we explored how the introduction of desaminotyrosine (DAT) and desaminotyrosyl tyrosine (DATT) linked to lysine residues of gelatin influenced the kinetics and thermodynamic equilibrium of the helicalization process of single and triple helices following different drying conditions. Drying at a temperature above the helix-to-coil transition temperature of gelatin (T > T(c), called v(short)) generally resulted in gelatins with relatively lower triple helical content (X(c,t) = 1-2%) than lower temperature drying (T < T(c), called v(long)) (X(c,t) = 8-10%), where the DAT(T) functional groups generally disrupted helix formation. While different helical contents affected the thermal transition temperatures only slightly, the mechanical properties were strongly affected for swollen hydrogels (E = 4-13 kPa for samples treated by v(long) and E = 120-700 kPa for samples treated by v(short)). This study shows that side group functionalization and different drying conditions are viable options to control the helicalization and macroscopic properties of gelatin-based materials.

Copolymer Networks From Oligo(ε-caprolactone) and n-Butyl Acrylate Enable a Reversible Bidirectional Shape-Memory Effect at Human Body Temperature

Exploiting the tremendous potential of the recently discovered reversible bidirectional shape-memory effect (rbSME) for biomedical applications requires switching temperatures in the physiological range. The recent strategy is based on the reduction of the melting temperature range (ΔT m ) of the actuating oligo(ε-caprolactone) (OCL) domains in copolymer networks from OCL and n-butyl acrylate (BA), where the reversible effect can be adjusted to the human body temperature. In addition, it is investigated whether an rbSME in the temperature range close or even above Tm,offset (end of the melting transition) can be obtained. Two series of networks having mixtures of OCLs reveal broad ΔTm s from 2 °C to 50 °C and from -10 °C to 37 °C, respectively. In cyclic, thermomechanical experiments the rbSME can be tailored to display pronounced actuation in a temperature interval between 20 °C and 37 °C. In this way, the application spectrum of the rbSME can be extended to biomedical applications.

The role of the amorphous phase in the re-crystallization process of cold-crystallized poly(ethylene terephthalate)

The process of re-crystallization in poly(ethylene terephthalate) is studied by means of X-ray diffraction (SAXS and WAXS) and dynamical mechanical thermal analysis. Samples cold-crystallized for 9h at the temperatures Tc = 100 fcir#circ;C and Tc = 160 fcir#circ;C, i.e. in the middle of the

Direct mapping of fiber diffraction patterns into reciprocal space

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Polymer Micronetworks with Shape-Memory as Future Platform to Explore Shape-Dependent Biological Effects

relaxation region and close to its upper bound, respectively, are analyzed. During heating from room temperature, a structural rearrangement of the stacks is always found at Tr ≃ Tc + 20 fcir#circ;C. This process is characterized by a decrease of the linear crystallinity, irrespective of Tc; on the other hand, the WAXS crystallinity never increases with T below Tc+30fcir#circ;C. The lamellar thickness in the low-Tc sample decreases significantly after the structural transition, whereas in the high-Tc sample the lamellar thickness remains almost unchanged. In both, high- and low-Tc, the interlamellar thickness increases above Tr. Moreover, the high-Tc sample shows a lower rate of decrease of the mechanical performance with increasing T as the threshold Tr is crossed. This result is interpreted in terms of the formation of rigid amorphous domains where the chains are partially oriented. The presence of these domains would determine i) the stabilization of the crystalline lamellae from the thermodynamic point of view and ii) the increase of the elastic modulus of the amorphous interlamellar regions. This idea is discussed by resorting to a phase diagram. An estimation of the chemical-potential increase of the interlamellar amorphous regions, due to the enhancement of the structural constraints hindering segmental mobility, is offered. Finally, previous calculations developed within the framework of the Gaussian chain model (F.J. Baltá Calleja et al., Phys. Rev. B 75, 224201 (2007)) are used here to estimate the degree of chain orientation induced by the structural transition of the stacks.

Nanostructural changes in crystallizable controlling units determine the temperature-memory of polymers

On the basis of the concept of Polanyi [Z. Phys. (1921), 7, 149–180], the mapping of fiber diffraction patterns into reciprocal space is revisited. The result is a set of concise mapping relations that does not contain any approximations. This set permits the design of a direct method that, in principle, does not require refinement of mapping parameters even for patterns of tilted fibers. The method is unsuitable for diffuse scattering patterns. If inaccuracies of two pixels can be tolerated, a pattern is automatically mapped into reciprocal space in real time. The method is proposed for the processing of the extensive sets of patterns that are recorded in time-resolved wide-angle X-ray diffraction investigations of polymer materials.

Thermally-Induced Triple-Shape Hydrogels - Soft Materials Enabling Complex Movements.

Polymer micronetworks allowing stimuli-induced, predefined, and spatially directed shape shifts. The temperature-induced on-demand switching of shape is introduced as a function of polyester carriers. With their adjustable -switching temperature, micronetworks may serve as a model system to explore static and dynamic shape effects in biological systems.

Non-Continuously Responding Polymeric Actuators

Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 °C related to a broad melting transition (∼100 °C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (Tdeform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 °C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low Tdeform (<50 °C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.

Extractable Free Polymer Chains Enhance Actuation Performance of Crystallizable Poly(ε-caprolactone) Networks and Enable Self-Healing

Shape-memory hydrogels enable directed movements of a specimen in response to temperature, whereby crystallizable switching segments incorporated as side chains resulted in constant degrees of swelling during the shape-memory cycle. Here we report about hydrogels exhibiting a thermally induced triple-shape effect that allows complex movements of soft materials with two almost independent shape changes. Potential applications for those soft triple-shape materials are two-step self-unfolding devices or temperature-sensitive hydrogel actuators, for example, smart valves for flow rate control in aqueous media. Series of hydrogels with two different hydrophobic crystallizable switching segments were prepared. The degrees of swelling of the triple-shape hydrogels were not affected for different shapes or temperatures, which avoided in this way interferences on the shape shifts. During the two-step programming procedure, two distinct shapes can be implemented as reflected by shape fixity ratios of generally >50%. Structural analysis of the switching domains during the triple-shape cycle by means of X-ray scattering indicates that longer side chains gain lower orientation after deformation and that shorter side chains orient perpendicular to the hydrophilic main chain. Furthermore, it is observed that increased orientation of the switching domains is not a key requirement for adequate shape fixity and recovery ratios of the triple-shape effect in hydrogels, thus longer side chains can be utilized as switching segments in other shape-memory hydrogels.