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Spatiotemporal Sequence of Interdependent Nucleation Mechanisms in Ultrathin Polymer Films

Da Huang, Rana Bakhshi, Raoul M. D'Anselme, Günter Reiter. Macromolecules, published online

Employing defined starting conditions of ultrathin molten poly(ethylene oxide) films on model solid substrates, we investigated the spatiotemporal sequence of interdependent mechanisms of crystal nucleation. Due to the limited number and the preferred conformation of polymer chains parallel to the substrate, primary nucleation favored edge-on lamellar crystals, which indirectly induced other subsequent nucleation pathways, enabled through the molten polymer chains accumulated at their peripheral fold surfaces. Both additional edge-on lamellar crystals and branched flat-on lamellar crystals were initiated. For long-chain polymers, spatial correlations between lamellar crystals across intervening noncrystalline regions were established through polymer chains incorporated within neighboring lamellae. (more...)


Nonmonotonic Variation of the Preferential Orientation of Lamellar Crystals in Films of Cold-Crystallized Poly(l-lactide) of Increasing Thickness and Molecular Weight

Decai Lin, Zebin Su, Yuxiang Chen, Jianquan Xu, Günter Reiter, Cuiyun Zhang, Xinping Wang. Macromolecules  59 (2026) 4970–4981

Using infrared reflection–absorption spectroscopy and atomic force microscopy, we revealed that polymer–substrate interactions, chain length, and film thickness critically influenced the morphology and orientation of lamellar crystals of poly(l-lactide) (PLLA) grown at a constant temperature. In contrast to the often-observed monotonic change from preferentially flat-on to edge-on crystals upon increasing film thickness, an unprecedented nonmonotonic change in the dominating orientation of lamellar crystals from edge-on to flat-on and back to edge-on was observed. In the thinnest films, size confinement and adsorption-induced alignment of the chains favored the nucleation and growth of edge-on lamellar crystals. Enhanced polymer–substrate interactions promoted the formation of edge-on lamellar crystals in the thinnest films with a higher molecular weight. (more..)


Properties of Charged Conjugated Polymers Deposited by Electrospraying on Substrates with an Insulating Oxide Layer

Anmol Arya, Solomon L. Joseph, Francois Vonau, Jean-Luc Bubendorff, Silvia Siegenführ, Laurent Simon, Günter Reiter. J. Phys. Chem. C 2026, 130, 5536–5546

In the course of electrospraying in a vacuum, polymers acquire electric charges, which are distributed along their backbone. Here, we demonstrate that these charges have a strong impact on the molecular ordering and spectroscopic properties of conjugated polymers when deposited on substrates with an insulating oxide layer. To this end, we electrosprayed varying amounts of poly(3-hexylthiophene) (P3HT) onto silicon substrates with oxide layers of different thickness. The resulting morphologies were explored by atomic force microscopy. The corresponding spectroscopic properties, including their changes in time upon illumination, were derived from photoluminescence (PL) measurements. On insulating substrates, charges were retained on the polymer chains, causing long-range electrostatic repulsion and the formation of largely separated droplet-like objects containing multiple chains. These objects exhibited significant PL intensities for photons with a wavelength (λ) less than ca. 600 nm, suggesting the lack of π–π stacking interactions between P3HT chains. (more...)


Reversible Metamorphosis of a Conjugated Polymer Induced by Photoexcitation

Solomon Joseph, Anmol Arya, Günter Reiter. Advanced Photonics Research 7 (2026) e202500311

Optoelectronic properties of materials are frequently examined through spectroscopic tools based on the absorption and emission of (visible) photons. Typically, one assumes that these transient characterization processes do not cause observable change of these properties because of the low power of the employed light sources. However, for flexible conjugated polymers in a medium of low viscosity, it is decidedly unclear whether photoexcitation of electrons on the backbone of a long polymer chain has an influence on macromolecular conformations and the corresponding intermolecular interactions. Here, we provide clear experimental evidence that continuous absorption of photons progressively causes persistent changes in the spectroscopic properties of conjugated polymers, accompanied by microscopically observable changes in their spatial distribution within a low-viscosity matrix. By contrast, all these changes were completely absent in nonilluminated parts of the same sample.(more...)


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. (more...)
 

Liste der Veröffentlichungen

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)
Condensed Matter Physics: Crystals, Liquids, Liquid Crystals, and Polymers
Gert Strobl. Springer 2003, ISBN 978-3540003533
Role of the entangled amorphous network in tensile deformation of semicrystalline polymers
Y. F. Men, J. Rieger, G. Strobl. Physical Review Letters 91, 095502 (2003)
Photonic defect modes in cholesteric liquid crystal films
J. Schmidtke and W. Stille. Eur. Phys. J. E 12, 553 (2003)
Characteristic variations in the effect of diluents on polymer crystallization and melting observed for a sample of poly (ethylene-co-octene)
Barbara Heck, Gert Strobl, Michael Grasruck. Eur. Phys. J. E 11, 117-130 (2003)
Editorial: Special issue on Properties of Thin Polymer Films
Günter Reiter (Editor) and James Forrest (Guest Editor). Eur. Phys. J. E 8, 101 (2002)
Morphological Phase Transitions in Spontaneous Dewetting of Thin Films on Homogeneous and Heterogeneous Surfaces
A. Sharma, G. Reiter. Phase Transitions 75, 377-399 (2002)
Pattern formation and ordering in thin films of crystallisable block copolymers
Günter Reiter, Gilles Castelein, Jens-Uwe Sommer. Macromol. Symp. 183, 173–178 (2002)
Some relevant parameters affecting the glass transition of supported ultra-thin polymer films
Y. Grohens, L. Hamon, G. Reiter, A. Soldera, Y. Holl. Eur. Phys. J. E 8, 217-224 (2002)
Are changes in morphology clear indicators for the glass transition in thin polymer films? Tentative ideas
Günter Reiter. Eur. Phys. J. E 8, 251-255 (2002)
The melting line, the crystallization line, and the equilibrium melting temperature of isotactic polystyrene
M. Al-Hussein, G. Strobl. Macromolecules 35, 1672-1676 (2002)
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