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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

Chances and Challenges in Europe
G. Reiter, N. Hadjichristidis, M. Möller. Nature Materials 2, 67-69 (2003)
Effet autophobe et démouillage des couches minces de polymères
G. Reiter. L’Actualité Chimique, Janvier 2003, p. 12-17
Polymer Crystallization on Pre-patterned Substrates
G. Dorenbos, J.-U. Sommer, G. Reiter. J. Chem. Phys. 118, 784-791 (2003)
Thermodynamics of Formation, Reorganization and Melting of Confined Nanometer-sized Polymer Crystals
Andreas Röttele,Thomas Thurn-Albrecht, Jens-Uwe Sommer, Günter Reiter. Macromolecules 36, 1257-1260 (2003)
Outlook and open questions: A personal view
Günter Reiter and Jens-Uwe Sommer. In Lecture Notes in Physics: "Polymer Crystallization: Observations, Concepts and Interpretations". Eds. Jens-Uwe Sommer and Günter Reiter, p.378-382, 2003
A Generic Model for Growth and Morphogenesis of Polymer Crystals in Two Dimensions
Jens-Uwe Sommer and Günter Reiter. In Lecture Notes in Physics: "Polymer Crystallization: Observations, Concepts and Interpretations". Eds. Jens-Uwe Sommer and Günter Reiter, p.153-176, 2003
Crystallization of Polymers in Thin Films: Model experiments
Günter Reiter, Gilles Castelein and Jens-Uwe Sommer. In Lecture Notes in Physics: "Polymer Crystallization: Observations, Concepts and Interpretations". Eds. Jens-Uwe Sommer and Günter Reiter, p.131-152, 2003
Polymer Crystallization: Obervations, Concepts and Interpretations
Editors: Jens-Uwe Sommer and Günter Reiter. Lecture Notes in Physics 606 (2003), Springer Berlin/Heidelberg, ISSN 1616-6361
Dewetting of thin polymer films at temperatures close to the glass transition
G. Reiter, M. Sferrazza, P. Damman. Eur. Phys. J. E 12, 133–138 (2003)
Editorial on "Focus point": Unstable thin films
A.M. Donald, J.F. Joanny,M. Moller,G. Reiter. Eur. Phys. J. E 12, 359-360 (2003)
Crystal growth rates of diblock copolymers in thin films: Influence of film thickness
G.Reiter, L.Vidal. Eur. Phys. J. E 12, 497-505 (2003)
Self-destruction and dewetting of thin polymer films: the role of interfacial tensions
G. Reiter, R. Khanna, A. Sharma. J. Phys. Condensed Matter 15 (2003) S331-S336
Crystallization of s-polypropylene from the glassy state: Indications for a multistage process
M. Grasruck, G. Strobl. Macromolecules 36, 86-91 (2003)
A molar mass induced transition in the yielding properties of linear polyethylene
Qiang Fu, Yongfeng Men, Gert Strobl. Polymer 44, 1941-1947 (2003)
Understanding of the tensile deformation in HDPE/LDPE blends based on their crystal structure and phase morphology
Qiang Fu, Yongfeng Men, Gert Strobl. Polymer 44, 1927-1933 (2003)
Critical strains in poly(epsilon-caprolactone) and blends with poly(vinyl methyl ether) and poly(styrene-co-acrylonitrile)
Yongfeng Men, Gert Strobl. Macromolcules 36, 1889-1898 (2003)
On the mechanisms of recrystallization after melting in semicrystalline polymers: The effect of the initial melt state
M. Al-Hussein, G. Strobl. Journal of Macromolecular Science - Physics B42, 677-685 (2003)
Fluorescence of a dye-doped cholesteric liquid crystal film in the region of the stop band: theory and experiment
J. Schmidtke and W. Stille. Eur. Phys. J. B 31, 179 (2003)
Investigating polymer crystallization by time-dependent light scattering: a direct approach in the data analysis applied for s-polypropylene
Anke Hoffmann, Gert Strobl. Polymer 44, 5803-5809 (2003)
Defect Mode Emission of a Dye Doped Cholesteric Polymer Network
J. Schmidtke, W. Stille, H. Finkelmann. Phys. Rev. Lett. 90, 083902 (2003)
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