Unusual crystals of poly(ε-caprolactone) by unusual crystallisation: The effects of rapid cooling and fast solvent loss on the morphology, crystal structure and melting

Sanandaji, Nima; Ovaskainen, Louise; Gunnewiek, Michel Klein; Vancso, Gyula J.; Hedenqvist, Mikael S.; Yu, Shun; Eriksson, Lars; Roth, Stephan V.; Gedde, Ulf W.

doi:10.1016/j.polymer.2013.01.014

Cited by 16 publications

(12 citation statements)

References 16 publications

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“…Thus, an optimized reciprocal space resolution of the relevant nanostructures can be obtained by selecting a suitable sample-detector distance. As a brief remark, we will not go into the details of diffraction and wide-angle scattering, used to obtain information on the crystalline structure of the layers, see, e.g., [ 151 , 152 , 153 ].…”

Section: Combining Grazing Incidence X-ray Scattering and Sputter mentioning

confidence: 99%

Investigating Polymer–Metal Interfaces by Grazing Incidence Small-Angle X-Ray Scattering from Gradients to Real-Time Studies

Schwartzkopf

Roth

2016

Nanomaterials

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Tailoring the polymer–metal interface is crucial for advanced material design. Vacuum deposition methods for metal layer coating are widely used in industry and research. They allow for installing a variety of nanostructures, often making use of the selective interaction of the metal atoms with the underlying polymer thin film. The polymer thin film may eventually be nanostructured, too, in order to create a hierarchy in length scales. Grazing incidence X-ray scattering is an advanced method to characterize and investigate polymer–metal interfaces. Being non-destructive and yielding statistically relevant results, it allows for deducing the detailed polymer–metal interaction. We review the use of grazing incidence X-ray scattering to elucidate the polymer–metal interface, making use of the modern synchrotron radiation facilities, allowing for very local studies via in situ (so-called “stop-sputter”) experiments as well as studies observing the nanostructured metal nanoparticle layer growth in real time.

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Section: Combining Grazing Incidence X-ray Scattering and Sputter mentioning

confidence: 99%

Investigating Polymer–Metal Interfaces by Grazing Incidence Small-Angle X-Ray Scattering from Gradients to Real-Time Studies

Schwartzkopf

Roth

2016

Nanomaterials

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“…A particularly striking phenomenon is the occasional appearance of curved habits. Solution-grown crystals of polyethylene (PE) [5], among other polymers, such as polyethylene oxide (PEO) [6], poly(vinylidene fluoride) (PVDF) [7] and poly--caprolactone (PCL) [8] can exhibit curved habits. In linear PE single crystals, curved {100} faces are seen at low supercooling (T), as the lozenge crystals {110} faces are truncated by the slow growth of curved {100} faces.…”

Section: Introductionmentioning

confidence: 99%

New habits in branched polyethylene single crystals

Vega

Müller

Martínez‐Salazar

2016

European Polymer Journal

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Faceted polymer single crystals obtained from solution have been examined for decades. Most of the studies have been performed with linear polyethylene. It is well known that solution-grown linear polyethylene single crystals may exhibit different and often complex morphologies and habits. However, the effect of molecular architecture (i.e., short chain branching) in the morphology of the single crystals remains practically unexplored. At the highest crystallization temperature investigated, the shape of the crystals is lozenge-like, but with curved and slightly truncated {110} faces. As the crystallization temperature decreases, strong changes in the width-to-length ratio and, consequently in the characteristic angles of the single crystal occur. Interestingly, the single crystals obtained at the lowest crystallization temperature explored exhibit a nearly square shape. This phenomenon has not yet been observed in linear high molecular weight polyethylene, for which the characteristic lozenge habit with straight {110} faces is retained as crystallization temperature decreases. The application of the Shcherbina and Ungar approach to fit the unusual shapes of the branched PE single crystals obtained in this work requires a strong decrease in the ratio of the rates of propagation to the right and to the left of the growth edge. This result is probably linked to different steric conditions of chain attachments into non-equivalent niches induced by the presence of branches.

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“…Under various conditions, it is well established that PCL tends to form six-sided hexagonal crystals [ 108 ]. The techniques used for SCs production contain several steps, they are time-consuming, and they are generally very elaborate.…”

Section: Resultsmentioning

confidence: 99%

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2021

Polymers

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End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional “hydrophobic amphiphile”, was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a “block-molecule”. According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL’s propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl3 at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

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Unusual crystals of poly(ε-caprolactone) by unusual crystallisation: The effects of rapid cooling and fast solvent loss on the morphology, crystal structure and melting

Cited by 16 publications

References 16 publications

Investigating Polymer–Metal Interfaces by Grazing Incidence Small-Angle X-Ray Scattering from Gradients to Real-Time Studies

Investigating Polymer–Metal Interfaces by Grazing Incidence Small-Angle X-Ray Scattering from Gradients to Real-Time Studies

New habits in branched polyethylene single crystals

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

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