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The size of critical secondary nuclei of polymer crystals does not depend on supersaturation 

Yang Liu, Zhiqi Wang, Yao Zhang, Tianyu Wu, Tianze Zheng, Bao Hua Guo, Günter Reiter, Jun Xu. Nature Communications 16 (2025) 3773

It is still a great challenge to determine the size of critical nuclei, which is crucial for a comprehensive understanding of crystallization and for testing the controversial crystallization theories. Here, we propose a method to determine the size of critical secondary nuclei on growth faces of poly(butylene succinate) single crystals in solution, basing on the probability of statistically selecting crystallizable units in random copolymers. In a dilute solution and for a given crystallization temperature, we reveal that the size of critical secondary nuclei was independent of supersaturation, contrary to the well-accepted prediction of existing theories which expect that the size of the critical nucleus increases with decreasing supersaturation. Accounting correctly for the dilution-caused change in the steady-state concentration of clusters of various sizes, we remedy inconsistencies of existing theoretical approaches in deriving the correct size of critical secondary nuclei in solution being independent of supersaturation. (more...)


Selective Dissolution as a Tool for Detecting Spatial Variations in the Degree of Metastability within Lamellar Polymer Crystals

Binghua Wang, Hailong Zou, Xuchen Wang, Changyu Shen, Jingbo Chen, Günter Reiter, Bin Zhang. Nature Communications 16 (2025) 3275

The dissolution of polymer crystals often proceeds at rates varying in time and space. Here, using low molecular weight poly(ethylene oxide) as a model polymer, we exploit step-wise selective dissolution for unveiling how spatial variations in metastability are generated during the growth of lamellar polymer single crystals. The dissolution velocity along defined crystal faces is constant, but ca. 5 times faster for rough than for smooth faces. From the temperature dependence of dissolution, we derive detachment energies of 420 ± 40 kJ/mol and 650 ± 50 kJ/mol for rough and smooth faces, respectively, suggesting that on a rough face polymer chains have ca. 1/3 less neighboring molecules to interact with. The observed high values of the activation energy indicate that, for dissolving a polymer crystal, the progressive detachment of whole chains is indispensable. Our study reveals a strong relation between growth kinetics and the resulting metastability of polymer crystals. (more...)


London dispersion forces and steric effects within nanocomposites tune interaction energies and chain conformation

Baode Zhang, Snežana D. Zarić, Sonja S. Zrilić, Iosif Gofman, Barbara Heck, Günter Reiter. Communications Chemistry 8 (2025) 21

baode.jpgThe interplay between attractive London dispersion forces and steric effects due to repulsive forces resulting from the Pauli principle often determines the geometry and stability of nanostructures. Aromatic polyimides (PI) and carbon nanotubes (CNT) were chosen as building blocks as two components in the hetero delocalized electron nanostructures. Two PIs, having the same diamine part and different linkage substituents between two phenyl rings of dianhydride part, one linked with ether bond (C-O-C) (OPI), the other with C-(CF3)2 (FPI), were investigated. Surprisingly, two CNT/PI nanocomposites show distinct failure mode from CNT yielding to CNT pull-out failure. Calculation of the interaction energy and chain conformations of each PI upon CNT was performed by accurate density functional theory (DFT) calculations and molecular dynamic simulation (MDS). (more...)


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...) 


 

Liste der Veröffentlichungen

From holes to drops to toroids: Conditions for the transcription of surface patterns into three-dimensional morphologies via rim instabilities in the course of dewetting
Samer Al Akhrass, Laurent Vonna and Günter Reiter. In: Polymer Surfaces in Motion: Unconventional Patterning Methods, Eds. Juan Rodriguez-Hernandez and Carlos Drummond. Springer 2015
Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States
Sivasurender Chandran, Stefanie Dold, Amaury Buvignier, Kai-Steffen Krannig, Helmut Schlaad, Günter Reiter, and Renate Reiter. Langmuir 2015, 31, 6426−6435. DOI: 10.1021/acs.langmuir.5b01212
High Temperature Stability of Dewetting-Induced Thin Polyethylene Filaments
Bin Zhang, Jingbo Chen, Paul Freyberg, Renate Reiter, Rolf Mülhaupt, Jun Xu, Günter Reiter. Macromolecules 48, 1518–1523 (2015)
Triangular dewetting by symmetry breaking in blends of stiff and flexible polymers
Paul Freyberg. Inaugural-Dissertation zur Erlangung des Doktorgrades der Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2015
Conductive atomic force microscopy measurements on organic nanocrystals
Sven Renkert. Master Thesis, Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2014
The influence of the additive composition on degradation induced changes in poly(ethylene-co-vinyl acetate) during photochemical aging
Angelika Beinert, Cornelia Peike, Ines Dürr, Michael D. Kempe, Günter Reiter, Karl-Anders Weiß. 29th European PV Solar Energy Conference and Exhibition, 22-26 Sept. 2014, Amsterdam, The Netherlands
Wie kristallisieren Polymere?
Gert Strobl. Physik Journal 13, 47-50 (2014)
The Crucial Role of Cadmium Acetate-Induced Conformational Restriction in Microscopic Structure and Stability of Polystyrene-block-Polyvinyl pyridine Thin Films
Feifei Xue, Hongfei Li, Jichun You, Conghua Lu, Günter Reiter, Shichun Jiang. Polymer 55, 5801-5810 (2014)
Molecular Weight Dependent Changes in Morphology of Solution Grown Polyethylene Single Crystals
Bin Zhang, Jingbo Chen, Moritz C. Baier, Stefan Mecking, Renate Reiter, Rolf Mülhaupt, Günter Reiter. Macrom. Rapid Comm. 36, 181-189 (2015)
Annealing-Induced Periodic Patterns in Solution Grown Polymer Single Crystals
Bin Zhang, Jingbo Chen, Hui Zhang, Moritz C. Baier, Stefan Mecking, Renate Reiter, Rolf Mülhaupt, Günter Reiter, RSC Advances 5, 12974 (2015)
Anisotropic Photophysical Properties of Highly Aligned Crystalline Structures of a Bulky Substituted Poly(thiophene)
Yingying Wang, Barbara Heck, Daniel Schiefer, John O. Agumba, Michael Sommer, Tao Wen, and Günter Reiter. ACSMacroLett. 3, 881-885 (2014)
Cellulose nanocrystals’ production in near theoretical yields by 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) – mediated hydrolysis
Jia Mao, Barbara Heck, Günter Reiter, Marie-Pierre Laborie. Carbohydrate Polymers 117, 443–451 (2015)
Correlating polymer crystals via self-induced nucleation
Hui Zhang, Muhuo Yu, Bin Zhang, Renate Reiter, Maximilian Vielhauer, Rolf Mülhaupt, Jun Xu, Günter Reiter. PhysRevLett 112, 237801 (2014)
Nickel Catalyst with a Hybrid P, N Ligand for Kumada Catalyst Transfer Polycondensation of Sterically Hindered Thiophenes
Daniel Schiefer, Tao Wen, Yingying Wang, Pierre Goursot, Hartmut Komber, Ralf Hanselmann, Pierre Braunstein, Günter Reiter, Michael Sommer. ACSMacroLett. 3, 617-621 (2014)
Tunneling Spectroscopy Measurements on Hydrogen-Bonded Supramolecular Polymers
François Vonau, Dominique Aubel, Laurent Bouteiller, Roozbeh Shokri, Günter Reiter, Olga Guskova, Laurent Simon. Nanoscale 6, 8250 (2014)
Pattern Formation on Single Crystals of Isotatic Polystyrene in Thin Films
Hui Zhang. Inaugural-Dissertation zur Erlangung des Doktorgrades der Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2014
Investigation of Structure Formation and Reorganization of Polymer Crystals
Bin Zhang. Inaugural-Dissertation zur Erlangung des Doktorgrads der Fakultät für Chemie und Pharmazie, 2014
Anisotropic charge transport in large single crystals of π-conjugated organic molecules
Wael Hourani, Khosrow Rahimi, Ioan Botiz, Felix Peter Vinzenz Koch, Günter Reiter, Peter Lienerth, Thomas Heiser, Jean-Luc Bubendorff, and Laurent Simon. Nanoscale 6, 4774 (2014)
Crystallization of Poly(γ-benzyl L-glutamate) in Thin Film Solutions: Structure and Pattern Formation
Kaiwan Jahanshahi, Ioan Botiz, Renate Reiter, Ralf Thomann, Barbara Heck, Roozbeh Shokri, Werner Stille and Günter Reiter. Macromolecules 46, 1470-1476 (2013)
Light absorption of poly(3-hexylthiophene) single crystals
Khosrow Rahimi, Ioan Botiz, John O. Agumba, Sajedeh Motamen, Natalie Stingelin, Günter Reiter. RSC Adv. 4, 11121 (2014)
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