Nanocelluloses for Templates for Functional Matter · Nanocelluloses for Templates for Functional...

OLLI IKKALA academy professor

Department of Applied Physics,

Aalto University School of Science (formerly Helsinki University of Technology),

FIN- 00076 Aalto, Espoo, Finland,

Olli.Ikkala@aalto.fi

Nanocelluloses for Templates for Functional Matter

Self-assemblies and biomimetics

Congratulations!

Forest industry has a jewel of materials at hand: ”Sustainable steel”

Cellulose I crystal

•  Native cellulose I crystal modification • Parallel hydrogen bonded chains

•  Modulus ca. 130-150 GPa • Iwamoto, Kai, Isogai, Iwata, Biomacromolecules 2009 10 2571

•  Strength in the 2-6 GPa range • Saito, Kuramae, Wohlert, Berglund, Isogai, Biomacromolecules 2013, 14, 248

•  Very good mechanical properties ! • cf Kevlar, steel

Inspires to take a new perspective as a materials/polymer engineer

Content Types of nanocellulose

Rånby, Discuss. Faraday Soc. 1951, 11, 158 Revol, Giasson, Marchessault, Gray, Int. J. Biol. Macromol. 1992, 14, 170 Fleming,Gray, Matthews, Chem. Eur. J. 2001, 7, 1831

Turbak, Snyder, Sandberg, J. Appl. Polym. Sci. Polym. Symp. 1983, 37, 815 Pääkkö, Ankerfors, Kosonen, Nykänen, Ahola,Österberg, Ruokolainen, Laine, Larsson, Ikkala, Lindström, Biomacromolecules 2007, 8, 1934 Henriksson, Henriksson, Berglund, Lindström, Eur. Polym. J. 2007, 43, 3434

Zimmermann, Adv Eng Mat 2004 6754

Cellulose nanocrystals

Nanofibrillated cellulose Bacterial cellulose

Tunicates

Nanofibrillated cellulose forms strong gels

Cellulose nanofibrils form strong gels in water

Photograph: M Ankerfors, T Lindström/STFI

•  Strong gels •  Still flow easily

•  Classic applications •  Oil recovery, paints, concrete, etc

•  Advanced applications •  Biomedicine, stem cell growth •  Injectable

Pääkkö, Ankerfors, Kosonen, Nykänen, Ahola, Österberg, Ruokolainen, Laine, Larsson, Ikkala, Lindström, Biomacromolecules 2007 8, 1934 Bhattacharya, Malinen, Lauren, Lou, Kuisma, Kanninen, Lille, Corlu, GuGuen-Guillouzo, Ikkala, Laukkanen, Urtti, Yliperttula, J Contr Rel, 164 291 2012

Ultralightweight porous materials by drying

Aerogels

The nanocellulose aerogels are mechanically robust

Pääkkö, Silvennoinen, Vapaavuori, Nykänen, Ankerfors, Kosonen, Ruokolainen, Lindström, Berglund, Ikkala, Soft Matter, 2008, 4, 2492

•  Flexible ductile materials •  Unlike classic aerogels which are

brittle

Functionalized nanocellulose

aerogels

Magnetic actuating nanocellulose aerogels

Olsson, Azizi Samir, Salazar-Alvarez, Belova, Ström, Berglund, Ikkala, Nogués, Gedde, Nature Nanotech, 5, 584 (2010).

Combine the best of two worlds: Nanocellulose and Carbon nanotubes

Modulus 140 GPa Strength GPa´s Sustainable

Modulus 1000 GPa Strength 30-60 GPa Electrical

Sensing movement"

Wang, Anoshkin, Nasibulin, Korhonen, Seitsonen, Pere, Kauppinen, Ras, Ikkala, Adv Mat 2013

Titanium dioxide functionalization of nanocellulose

Semiconductor

Titanium dioxide coated nanocellulose aerogel

Kettunen (née Pääkkö), Silvennoinen, Houbenov, Nykänen, Ruokolainen, Sainio, Pore, Kemell, Ankerfors, Lindström, Ritala,. Ras, Ikkala, Adv Funct Mat 2011, 21 510

Nanometer thick coatings

Atomic layer deposition/chemical vapour deposition

Burn nanocellulose for hollow oxide nanofibers

Korhonen, Hiekkataipale, Malm, Karppinen, Ikkala, Ras, ACS Nano, 2011 , 5, 1967

Sensors, devices, as oxides are semiconductors

•  Absorb oil

•  Repel water

•  Float on water

Korhonen, Kettunen, Ras, Ikkala, ACS Applied Mat and Interf, 3, 1813 (2011).

Titanium dioxide-coated nanocellulose aerogels for oil-spills

Extremely water repellant materials

•  Spray-dried nanofibrillated cellulose •  Leads to surface patterns •  Coat with fluorinated surfactant •  Lotus-like superhydrophobic surface •  Water rolls off, dirt repellent, like lotus

Mertaniemi, Laukkanen, Teirfolk, Ikkala, Ras, RSC Advances, 2, 2882, (2012). .

Extremely water repellent surfaces using nanocellulose

Lotus

•  Classic applications of superhydrophobicity •  Dirt repellency, self-cleaning antifogging, anti-icing, etc

•  We have shown recently unforeseen new options •  Water based logic circuits (Advanced Materials 2012) •  Water based displays (Proc National Acad Sciences 2012) •  Droplet oscillators (Nature Communications 2013) •  Dynamic on surfaces (Science 2013)

•  They may lead new microfluidic devices

Future of extreme water repellancy

Functionalization of cellulose nanocrystals

Polymer coatings on cellulose nanocrystals: Tuning the properties

Majoinen, Walther, McKee, Kontturi, Aseyev, Malho, Ruokolainen, Ikkala, Biomacromolecules, 12, 2997, 2011

Well defined polymerization on cellulose nanocrystals: only recently identified Modular approaches demonstrated: relevant for applications

Electron microscopy

Filpponen, Kontturi, Nummelin, Rosilo, Kolehmainen, Ikkala, Laine, Biomacromolecules, 13, 736, 2012

Coating resolved !

Strong composites

Mimicking pearl of nacre

Learning  from  Nature  for  nanocomposites  

Laaksonen, Walther, Malho, Kainlauri, Ikkala, Linder, Angew Chem 2011 50 8688

Chitin nanofibers

Wu, Saito, Fujisawa, Fukuzumi, Isogai, Biomacromolecules 2012, 13, 1927

Pearl of nacre combines strength, stiffness, and toughness in a way that is difficult to achieve with manmade materials

Calcium carbonate nanosheets

Nanofibrillated cellulose/graphene

Protein glue

Nanofibrillated cellulose/nanoclay

Nanoclay content

Combine nanofibrillated cellulose and nanosheets

Strong macroscopic fibers based on native nanocellulose nanofibers

Iwamoto, Isogai, Iwata, Biomacromolecules, 2011, 12 831 Walther, Timonen , Díez, Laukkanen , Ikkala , Adv Mat, 2011, 23, 2924

Macroscopic fibers of nanocellulose

•  Excellent mechanical properties •  Can be functionalized

•  Electrically conducting •  Magnetic •  Drug release •  Patterned

Summary"

•  The paper industry has at hand nanocellulose •  Strong, functionalizable, sustainable

•  Totally new applications are at hand beyond the classic paper/cardboard “Next generation nanomaterial”

•  Need new expertizes, polymer chemistry, supramolecular chemistry, soft electronics, materials science, biology, analytical chemistry, materials physics, pharmacy,

•  Special high tech applications, new application connections •  Materials that are tough, strong, and stiff •  Various functionalizations

Specific challenge: Make tough! Solutions are now at hand!

Cracks propagate in a stable manner!

Funding acknowledgement

Finnish Center for Nanocellulose Technologies, UPM, Academy of Finland, TEKES Sustaincomp/EU NMP Designcell/Woodwisdom ERC Advanced Grant Center of Excellency (Ikkala, Laine, Linder, Penttila Aalto/VTT collaboration)