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Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy

Janko, Marek and Jocher, Michael and Boehm, Alexander and Babel, Laura and Bump, Steven and Biesalski, Markus and Meckel, Tobias and Stark, Robert W. (2015):
Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy.
In: Biomacromolecules, American Chemical Society, pp. 2179-87, 16, (7), ISSN 1525-7797, [Online-Edition: http://dx.doi.org/10.1021/acs.biomac.5b00565],
[Article]

Abstract

The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-meth-acrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.

Item Type: Article
Erschienen: 2015
Creators: Janko, Marek and Jocher, Michael and Boehm, Alexander and Babel, Laura and Bump, Steven and Biesalski, Markus and Meckel, Tobias and Stark, Robert W.
Title: Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy
Language: English
Abstract:

The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-meth-acrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.

Journal or Publication Title: Biomacromolecules
Volume: 16
Number: 7
Publisher: American Chemical Society
Divisions: 10 Department of Biology
10 Department of Biology > Membrane Dynamics
11 Department of Materials and Earth Sciences
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences > Material Science > Physics of Surfaces
Profile Areas
Profile Areas > Thermo-Fluids & Interfaces
Exzellenzinitiative
Exzellenzinitiative > Clusters of Excellence
07 Department of Chemistry
07 Department of Chemistry > Fachgebiet Makromolekulare Chemie
Zentrale Einrichtungen
Date Deposited: 28 Jul 2015 09:58
Official URL: http://dx.doi.org/10.1021/acs.biomac.5b00565
Funders: In addition, we gratefully acknowledge the Center of Smart Interfaces of the Technische Universitat Darmstadt for financial support., M.B. acknowledges financial support from the Verband der Deutschen Papierindustrie (VDP) within the INFOR programme (MAP NV164) and from the Bundesministerium fur Wirtschaft und Energie (BMWi) under AiF-IGF-grant no. 17919N "PhoreNast".
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