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Temperature dependence of crystal – melt coexistence for supported polyethylene filaments

Da Huang, Thorsten Hugel, Bizan N. Balzer, Günter Reiter. Nature Communications 16 (2025) 11127

The broken symmetry of molecular interactions at interfaces is causing that crystals are often covered by a thin liquid layer of their own melt. Such crystal–melt coexistence can be related to phenomena of surface premelting, secondary nucleation and melting point depression, particularly important for small systems. Here, we employed intermittent-contact mode atomic force microscopy imaging on nanoscopic semi-cylindrical filaments of polyethylene on a substrate to observe that these filaments contained a crystalline core bounded by molten regions of rather uniform width,  W_soft= (9 ± 2) nm at room temperature, which increased reversibly with temperature T. Filaments smaller than ca. 2∙W_soft (T) were completely molten. The values of W_soft (T) compared favorably with theoretically predicted characteristic length scales in the context of nucleation, surface premelting and the melting point depression of finite size crystals. Altogether, we show that these three phenomena are related and dominated by the intermolecular forces acting at crystal surfaces.


Crystallization of Layers of Strongly Adsorbed Poly(ethylene terephthalate) on Silicon Substrates

Liang Chen, Zhihang Bian, Xiaonan Li, Zhenwei Jiang, Jianquan Xu, Decai Lin, Guenter Reiter, Jichun You, Xinping Wang. Macromolecules 58 (2025) 12222–12230 

2025-rei-05.jpgWe examined the crystallization behavior of ultrathin layers of strongly adsorbed poly(ethylene terephthalate) (PET) chains on silicon substrates, yielding a characteristic morphology of uniquely curved dendritic polymer crystals. The observed curvature resulted from bent edge-on lamellar crystals from which terraced flat-on branched lamellar crystals grew essentially from the convex outer side. The degree of bending increased with decreasing crystallization temperature and increasing strength of polymer/substrate interactions. We propose that unbalanced stresses acting on the fold surfaces of PET lamellar crystals, probably induced by strong interactions with the substrate, were responsible for the observed curvature of the lamellar crystals. (more...)


Crystallization and Melting of Polyethylene Strongly Cross-linked in the Molten State 

Jingqing Li, Weihua Wang, Yunxiang Shi, Barbara Heck, Chuanfu Luo, Jesper de Claville Christiansen, Donghong Yu, Günter Reiter, Shichun Jiang. Soft Matter 21 (2025) 6422 

jiang2025.jpgWe examined the crystallization and melting behavior of highly cross-linked polyethylene (xPE) samples, including structural characterization of the resulting crystalline domains. Using γ-ray irradiation, cross-linking was performed in the molten state and not in the solid state. This approach assured a statistical and homogeneous distribution of the cross-link points. Upon increasing the radiation dose, the molecular weight of the strands connecting the cross-link points reached values even lower than that of the strands between physical entanglements. (more...)

 


 

Liste der Veröffentlichungen

Defect Structure and Molecular-Motion in 4 Modifications of Normal-Tritriacontane. 1. Study of Defect Structure in Lamellar Interfaces Using Small-Angle X-Ray-Scattering
G. Strobl, B. Ewen, E.W. Fischer, W. Piesczek. J. Chem. Phys. 61, 5257-5264 (1974)
An exactly solvable model for coherent and incoherent exciton motion
H. Haken and G. Strobl. Zeitschrift für Physik 262, 135-148 (1973)
Small-angle x-ray scattering experiments for investigating the validity of the two-phase model
G.R. Strobl, N. Müller. Journal of Polymer Science B - Polymer Physics 11, 1219-1233 (1973)
Determination of Lamellar Structure of Partially Crystalline Polymers by Direct Analysis of their Small-Angle X-Ray-Scattering Curves
G.R. Strobl. Journal of Applied Crystallography 6, 365-370 (1973)
Synthese und Eigenschaften molekulareinheitlicher n-Paraffine bis zum C140H282
W. Heitz, E.W. Fischer, R. Peters, T. Wirth, G. Strobl. Makromolekulare Chemie 162, 63 (1972)
Analyse von spaltverschmierten Kleinwinkelstreukurven lamellarer Strukturen
G.R. Strobl. Kolloid-Zeitschrift and Zeitschrift für Polymere 250, 1039-1046 (1972)
A New Method for Evaluating Slit-Smeared Small Angle X-Ray Scattering Data
G.R. Strobl. Acta Crystallographica A 26, 367-375 (1970)
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