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Effect of chemical structure on the crystallization kinetics of triple polymorphic high-sulfur-content polythioethers

Valentina Pirela, Leire Unanue, Justine Elgoyhen, Javier Ramos, Juan Francisco Vega, Agurtzane Mugica, Manuela Zubitur, Cuong Minh Quoc Le, Abraham Chemtob, Radmila Tomovska, Günter Reiter, Jaime Martín, Alejandro J. Müller. European Polymer Journal (2025) 113721

This work studies how the chemical structure of relatively similar high-sulfur alternating polythioether homopolymers (DMDS-alt-DVE, DMDS-alt-TEGDVE, and DMDS-alt-BDDVE) affects their structural properties, morphology, polymorphism, and crystallization kinetics. Differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM) experiments revealed a complex crystallization for the samples in which up to three different polymorphic phases were identified: a very low melting crystal form (VL-Tm form), a low melting crystal form (L-Tm form) and a high melting crystal form (H-Tm form), characterized by their corresponding melting temperature ranges and confirmed via Wide-Angle X-ray Scattering (WAXS). A coexistence of negative and positive spherulites was found, and their origin was revealed by atomic force microscopy (AFM), which showed how the lamellar arrangement varied in the samples from predominantly radial to a cross-hatched morphology. (more...)
 


Post-spin Stretch Improves Mechanical Properties, Reduces Necking, and Reverts Effects of Aging in Biomimetic Artificial Spider Silk Fibers

Gabriele Greco, Benjamin Schmuck, Fredrik G. Bäcklund, Günter Reiter and Anna Rising. ACS Appl. Polym. Mater.  6 (2024) 14342–14350

reiter-2024-05.jpgRecent biotechnological advancements in protein production and development of biomimetic spinning procedures make artificial spider silk a promising alternative to petroleum-based fibers. To enhance the competitiveness of artificial silk in terms of mechanical properties, refining the spinning techniques is imperative. One potential strategy involves the integration of post-spin stretching, known to improve fiber strength and stiffness while potentially offering additional advantages. Here, we demonstrate that post-spin stretching not only enhances the mechanical properties of artificial silk fibers but also restores a higher and more uniform alignment of the protein chains, leading to a higher fiber toughness. (more...)


Mechanistically Different Mechanochromophores Enable Calibration and Validation of Molecular Forces in Glassy Polymers and Elastomeric Networks

Raphael Hertel, Maximilian Raisch, Michael Walter, Günter Reiter, Michael Sommer. Angew. Chem. Int. Ed. 2024, e202409369

sommer.jpgSterically distorted donor-acceptor p‑systems, termed DA springs, can be progressively planarized under mechanical load causing a bathochromic shift of the photoluminescence (PL) spectrum. By combining theory and experiment, we here use a simple linear force calibration for two different conformational mechanochromophores to determine molecular forces in polymers from the mechanochromic shift in PL wavelength during multiple uniaxial tensile tests. Two systems are used, i) a highly entangled linear glassy polyphenylene and ii) a covalent elastomeric polydimethylsiloxane network. The mean forces estimated by this method are validated using known threshold forces for the mechanochemical ring-opening reactions of two different spiropyran force probes. The agreement between both approaches underlines that these DA springs provide the unique opportunity for the online monitoring of local molecular forces present in diverse polymer matrices.(more...)


 

Liste der Veröffentlichungen

Crystallization in diblock copolymer thin films at different degrees of supercooling
C. Darko, I. Botiz, G. Reiter, D.W. Breiby, J.W. Andreasen, S. V. Roth, D.-M. Smilgies, E. Metwalli, C.M. Papadakis. Phys. Rev. E 79, 041802 (2009)
Branched substituents generate improved supramolecular ordering in physisorbed molecular assemblies
F. Vonau, M. Linares, B. Isare, D. Aubel, M. Habar, L. Bouteiller, G. Reiter, V. Geskin, F. Zerbetto, R. Lazzaroni, L. Simon. J. Phys. Chem. C 113, 4955-4959 (2009)
Polymer crystallization under nano-confinement of droplets studied by molecular simulations
Wenbing Hu, Tao Cai, Yu Ma, Jamie K. Hobbs, O. Farrance, Günter Reiter. Faraday Discussions 143, 129-141 (2009)
Cloning Polymer Single Crystals through Self-seeding
Jianjun Xu, Yu Ma, Wenbing Hu, Matthias Rehahn, and Günter Reiter. Nature Materials 8, 348-353 (2009)
Structuring the Surface of Crystallizable Polymers with an AFM Tip
Cvetlin Vasilev, Günter Reiter, Khalil Jradi, Sophie Bistac, Marjorie Schmitt. In: "Scanning Probe Microscopy in Nanoscience and Nanotechnology" Part 3, Ed. Bharat Bhushan, "NanoScience and Technology" Series, Springer 2010, ISBN 978-3-642-03534-0
Visualizing properties of polymers at interfaces: Relations between molecular features and macroscopic behaviour
Günter Reiter. In “Soft Matter: Scattering, Imaging and Manipulation”, Volume IV: Imaging and Manipulation Techniques Eds.: R. Pecora, R. Borsali, Springer 2008, ISBN 978-1402044649
Some general remarks on crystallization in the presence of additives
Günter Reiter and Jean-Georges Barth. Elemente der Naturwissenschaft 92, 39-61 (2010)
Network swelling competing with translational entropy in autophobic polymer dewetting
W. Beziel, G. Reiter, E. Drockenmuller, R.-V. Ostaci, S. Al Akhrass, F. Cousin, M. Sferrazza. Europhysics Letters 90, 26008 (2010)
Processes of Ordered Structure Formation in Polypeptide Thin Film Solutions
Ioan Botiz, Helmut Schlaad, Günter Reiter. Adv. in Polymer Science, 242 (2011) 117-149
Multi-curvature liquid meniscus in a nanochannel: Evidence of interplay between intermolecular and surface forces
Pilnam Kim, Ho-Young Kim, Jae Kwan Kim, Günter Reiter, Kahp Y. Suh. Lab Chip 9, 3255-3260 (2009)
Self-assembled patterns from evaporating layered fluids
L. V. Govor, J. Parisi, G. H. Bauer, G. Reiter. Journal of Physics - Condensed Matter 21, 264015 (2009)
Dewetting as an investigative tool for studying properties of thin polymer films
Günter Reiter, Samer Al Akhrass, Moustafa Hamieh, Pascal Damman, Sylvain Gabriele, Thomas Vilmin, Elie Raphaël. Eur. Phys. J. - Special Topics 166, 165-172 (2009)
Characterizing and modeling the non-linear viscoelastic tensile deformation of a glass fiber reinforced polypropylene
J. Fritsch, S. Hiermaier, G. Strobl. Composites Science and Technology 69, 2460-2466 (2009)
Colloqium: Laws controlling crystallization and melting in bulk polymers
G. Strobl. Rev. Mod. Phys. 81, 1287-1300 (2009)
Deformation of cholesteric elastomers by uniaxial stress along the helix axis
Werner Stille. Eur. Phys. J. E 28, 57-71 (2009)
高分子物理学: 理解其结构和性质的基本概念
作者:(德国)G.斯特罗伯 译者:胡文兵 蒋世春 门永峰 北京:科学出版社 2009, ISBN 978-7-03-022441-5
Metastable Untwisted States in Cholesteric Elastomers
Werner Stille. Macromolecules 42, 7979-7981 (2009)
Gradient Interfaces in SBS and SBS/PS Blends and Their Influence on Morphology Development and Material Properties
Yi Thomann, Ralf Thomann, Alfred Hasenhindl, Rolf Mülhaupt, Barbara Heck, Konrad Knoll, Helmut Steininger, Kay Saalwächter. Macromolecules 42, 5684-5699 (2009)
Understanding crystal orientation in quasi-one-dimensional polymer systems
Yu Ma, Wenbing Hu, Jamie Hobbs, Guenter Reiter. Soft Matter 4, 540-543 (2008)
Oligonucleotide nanostructured surfaces: effect on Escherichia coli curli expression
Nicolas Cottenye, Francisco Teixeira Jr., Arnaud Ponche, Günter Reiter, Karine Anselme, Wolfgang Meier, Lydie Ploux, Corinne Vebert-Nardin. Macromolecular Bioscience 8, 1161-1172 (2008)
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