The doctoral dissertations of the former Helsinki University of Technology (TKK) and Aalto University Schools of Technology (CHEM, ELEC, ENG, SCI) published in electronic format are available in the electronic publications archive of Aalto University - Aaltodoc.
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Surface-Modified Nanoparticles for Ultrathin Coatings

Tiina Nypelö

Doctoral dissertation for the degree of Doctor of Science in Technology to be presented with due permission of the School of Chemical Technology for public examination and debate in Auditorium Puu2 at the Aalto University School of Chemical Technology (Espoo, Finland) on the 17th of February 2012 at 12 noon.

Overview in PDF format (ISBN 978-952-60-4499-6)   [3250 KB]
Dissertation is also available in print (ISBN 978-952-60-4498-9)

Abstract

Nanoparticle modification and their utilization in the modification of planar substrates were examined. Emphasis was placed on two topics: the control of layer structure during formation and the alteration of the wetting characteristics of modified surfaces. Layer formation was investigated by adsorbing nanoparticles with a distinct shape and charge onto a nanofibrillated cellulose (NFC) substrate. In addition, nanosized silica particles and NFC were adsorbed sequentially with an oppositely charged polyelectrolyte onto an NFC substrate in order to explore the structures achievable using layer-by-layer assembly. Evidently, the utilization of nanoparticles in layer formation demands the control of the nanoparticle dispersion stability and particle affinity to the substrate. When combining nanoparticles with other substances, the properties of the particles define the layer structure; large fibrils were able to form a stratified layer, while silica nanoparticles were able to penetrate the preceding layer and transform the structure into a uniform network of polyelectrolyte and nanoparticles.

The effect of nanoparticle surface modification on dispersion properties and on the structure and properties of the layers formed were also of interest. Modification of nanosized silica and precipitated calcium carbonate particles was conducted by treatment with oppositely charged substances. This treatment resulted in stable nanoparticle dispersions able to be further modified with hydrophobic sizing agents. In addition to enhanced stability and functionality, the polyelectrolyte treatment could be used to affect the interaction of the nanoparticles with the other dispersion constituents.

Wetting of a smooth and dense substrate was not affected by the nanoscale roughness caused by the nanoparticle coating on the substrate. In order to affect substrate hydrophobicity, chemical hydrophobicity was deemed necessary. The combination of modified nanoparticles and a hydrophobic emulsion resulted in a nanostructure able to change the wetting characteristics of a planar substrate. Treatment of a smooth substrate with a hydrophobic dispersion resulted in slightly enhanced surface hydrophobicity. On paper, the combination of micron and nanoscale roughness with chemical hydrophobicity resulted in a significant increase in hydrophobicity. The coatings consisted of a thin nanoparticle structure with evenly distributed particles. In addition to use as a paper surface treatment, a layer, consisting of inexpensive particles allowing simple surface modification, could be used to functionalize planar substrates and enable the use of paper as a sustainable substrate, even in applications beyond its traditional use.

This thesis consists of an overview and of the following 5 publications:

  1. Tiina Nypelö, Hanna Pynnönen, Monika Österberg, Jouni Paltakari, and Janne Laine. Interactions between inorganic nanoparticles and cellulose nanofibrils. Cellulose, accepted for publication.
  2. Jani Salmi, Tiina Nypelö, Monika Österberg, and Janne Laine. 2009. Layer structures formed by silica nanoparticles and cellulose nanofibrils with cationic polyacrylamide (C-PAM) on cellulose surface and their influence on interactions. BioResources, volume 4, number 2, pages 602-625.
  3. Tiina Nypelö, Monika Österberg, Xuejie Zu, and Janne Laine. 2011. Preparation of ultrathin coating layers using surface modified silica nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, volume 392, number 1, pages 313-321.
  4. Tiina Nypelö, Monika Österberg, and Janne Laine. 2011. Tailoring surface properties of paper using nanosized precipitated calcium carbonate particles. ACS Applied Materials & Interfaces, volume 3, number 9, pages 3725-3731.
  5. Lei Dong, Tiina Nypelö, Monika Österberg, Janne Laine, and Mikko Alava. 2010. Modifying the wettability of surfaces by nanoparticles: Experiments and modeling using the Wenzel law. Langmuir, volume 26, number 18, pages 14563-14566.

Keywords: nanoparticle adsorption, dispersion stability, surface modification, ultrathin coatings, layer-by-layer assembly, wetting

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© 2012 Aalto University

Last update 2012-10-31