Structural Order in Cellulose Thin Films Prepared from a Trimethylsilyl Precursor

Andrew Owen Fletcher Jones, Roland Resel, Benedikt Schrode, Fabio Eduardo Machado Charry, Christian Werner Röthel, Birgit Kunert, Ingo Salzmann, Eero Kontturi, David Reishofer, Stefan Spirk

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 Å. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.
Original languageEnglish
Number of pages7
JournalBiomacromolecules
DOIs
Publication statusE-pub ahead of print - 12 Dec 2019

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Cellulose films
Cellulose
Thin films
Polymers
Crystalline materials
Biopolymers
Molecules
Spin coating
Substrates
Synchrotron radiation
Nanocrystals
Diffraction patterns
Infrared spectroscopy
Atomic force microscopy
Diffraction
Vapors
X ray diffraction

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Structural Order in Cellulose Thin Films Prepared from a Trimethylsilyl Precursor. / Jones, Andrew Owen Fletcher; Resel, Roland; Schrode, Benedikt; Machado Charry, Fabio Eduardo; Röthel, Christian Werner; Kunert, Birgit; Salzmann, Ingo; Kontturi, Eero; Reishofer, David; Spirk, Stefan.

In: Biomacromolecules, 12.12.2019.

Research output: Contribution to journalArticleResearchpeer-review

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title = "Structural Order in Cellulose Thin Films Prepared from a Trimethylsilyl Precursor",
abstract = "Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 {\AA}. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.",
author = "Jones, {Andrew Owen Fletcher} and Roland Resel and Benedikt Schrode and {Machado Charry}, {Fabio Eduardo} and R{\"o}thel, {Christian Werner} and Birgit Kunert and Ingo Salzmann and Eero Kontturi and David Reishofer and Stefan Spirk",
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AU - Resel, Roland

AU - Schrode, Benedikt

AU - Machado Charry, Fabio Eduardo

AU - Röthel, Christian Werner

AU - Kunert, Birgit

AU - Salzmann, Ingo

AU - Kontturi, Eero

AU - Reishofer, David

AU - Spirk, Stefan

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N2 - Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 Å. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

AB - Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 Å. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

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