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COST Action FP1105 workshop:

Functional wood and cellulose-based materials

31.08. – 01.09.2015

EMPA Academy, Dübendorf, Switzerland

Local Organizers:

Tanja Zimmermann and Ingo Burgert

Agenda – Abstracts – List of Participants

Agenda

31st of August 2015

08:30 - 09:00 Registration (attendance list signature).

09:00 - 09:30 Welcome and introduction to the workshop by the Action chair, Philip

Turner

General information by the host

09:30 - 11:00 Session I: chair: Tomas Larsson

9:30 – 10:00 Keynote lecture

Lars Berglund: Mechanical behavior of nanocellulose-based materials

10:00 - 11:00 3 Presentations (15mins + 5mins)

Alexy Khakalo, Alexy Vishtal, Ilari Filpponen, Elias Retulainen, Janne Laine, Orlando Rojas: Extensible fibre networks for cellulose-based composite materials

Ida Poljansek, Vesna Žepic, Primoz Oven: Formation of properties of nanofibrillated cellulose-based composites

GiseIa Cunha, Meri Lundhal, Orlando Rojas: Hydrophobization of nanocellulose-based filaments for high performance materials

11:00 - 11:30 Coffee break

11:30 - 13:00 Session II: chair: Philip Turner


Olli Ikkala: Functional nanocelluloses using self-assemblies and supramolecular interactions


Ahu Gümrah Dumanli, Ullrich Steiner: Co-assembly of cellulose nanocrystals and high aspect ratio nanoparticles

Eduardo Robles, Asier M. Salaberria, Rene Herrera, Luis Serrano, Jalel Labidi, Susana C.M. Fernandes: Cellulose nanofibers films reinforced with chitin nanocrystals for fungal inhibition

Amit Rivkin, Tiffany Abitbol, Yuval Nevo, Ronen Verker, Shaul Lapidot, Anton Komarov, Stephen C. Veldhuis, Galit Zilberman, Meital Reches, Emily D. Cranston and Oded Shoseyov: Bionanocomposite films from Resilin-CBD bound to cellulose nanocrystals

13:00 - 14:00 Lunch

14:00 - 16:00 Session III: chair: Ingo Burgert


Orlando Rojas: Wood and nanocellulose: deconstruction and assembly via multiphase systems

Tobias Keplinger, Etienne Cabane, Ingo Burgert: Strategies for the modification and functionalization of wood cell walls for the development of functional wood-polymer hybrid materials

Jana Segmehl, Tobias Keplinger, Ingo Burgert: Hierarchical cellulosic bio scaffolds derived from wood using chemical delignification methods adapted from industry

15:00 – 16:00 Poster presentations (5 mins) Itan Preis, Yiftach Birger, Oded Shoseyov: Synthetic and mechanically improved cell wall made from nanocellulose, lignin and rubber like protein-resilin

Ezgi Bakirci, Miguel Gama: Studies on the diffusion across bacterial cellulose membranes

Jia Mao, Marie-Pierre Laborie: Current methods for cellulose nanocrystals preparation: comparative and critical assessment

Jiaqi Guo, Ilari Filpponen, Orlando Rojas: Protein separation using magnetically responsive cellulose nanocrystals

Hua Jin, Benjamin Wilson, Eero Kontturi, Tekla Tammelin, Maarit Karppinen: Hybrid thin films from ZnO and nanocellulose

R. Gleuwitz, C. Friedrich, M.P. Laborie: Phase behavior and miscibility in all-lignocellulose polymer blend systems

Tiago Dos Santos, Heiko Winter, Marie-Pierre Laborie: Alignment of cellulose nanocrystals into oat spelt arabinoxylan films

Wenchao Xiang, Kristian Salminen, Timo Lappalainen, Erkki Saharinen, Ilari Filpponen, Orlando J. Rojas: Foam forming with cellulosic fibers

Jaka Levanic, Primoz Oven, Ida Poljansek: Ester of polyol and tempo modified cellulose: preparation and characterization

Maryam Borghei, Elo Kibena, Leena-Sisko Johansson, Joseph Campell, Esko Kauppinen, Kaido Tammeveski, Orlando Rojas: Cellulose-based nitrogen doped carbon as oxygen reduction catalyst for fuel cells

Hesam Taheri, Marie-Pierre Laborie, Pieter Samyn: Effect of processing parameters on the rheological behavior and morphology of microfibrillated cellulose

16:00 -16:30 Coffee break

16:30 -17:30 3 Presentations (15mins + 5mins)

Franziska Grüneberger, Tina Künniger, Anja Huch, Martin Arnold, Ingo Burgert, Tanja Zimmermann: Nanofibrillated cellulose as additive for wood coatings

Alina Lozhechnikova, Monika Österberg: Sustainable surface modification of wood

Ling Wang, Julio Arboleda, Pirjo Kääriäinen, Tapani Vuorinen, Orlando Rojas: Wood meets art

17:30 - 18:30 Poster session & drinks

19:30 - Dinner

1st of September 2015

08:30 - 09:00 Registration and Reimbursement Forms collection.

09:00 - 10:30 Session IV: chair: Pasi Kallio


Vincent Bulone: Cell wall polysaccharides biosynthesis in eukaryotes and materials applications


Hua Jin, Robin H.A. Ras, Olli Ikkala: Functional materials from nanocellulose

Hatem Abushammala, Ingo Krossing, Marie-Pierre Laborie: Novel ionic liquid-mediates production of cellulose nanocrystals directly from wood

P. Orsolini, P. Tingaut, T. Zimmermann, W.R. Caseri: Characterization of pore size distribution in nanofibrillated cellulose-based membranes: assessment of two porosimetry techniques.

10:30 - 11:00 Coffee break

11:00 - 13:05 Session V: chair: Manuel Mikczinski


M.-P. Laborie, M. Brioude, H. Haidara, L. Vonna , V. Roucoules: On the nanostructuring role of cellulose nanocrystals on maleic anhydride plasma polymer films

Linda Vecbiskena, Laura Vikele, Linda Rozenberga: Designing and evolution of cellulose-based nanofillers–doped chitosan films

Wenwen Fang, Eero Kontturi, Timo Laaksonen, Markus Linder, Päivi Laaksonen: Dispersion and functionality of cellulose nanocrystals

Juan M. Buffa, María Alejandra Grela, Mirta I. Aranguren, Verónica L. Mucci: Study of kinetics of TEMPO-mediated oxidation of nanocellulose by ESR

12:20 - 13:05 3 STSMs Presentations

Florian Zikeli, Heiko Lange, Claudia Crestini: Lignin modification with carbene chemistry

Carmen-Mihaela Popescu: Wood structure – moisture content relations in unmodified and chemically modified wood

O. Sevastyanova, O. Gordobil, B. Podkoscielna, J. Labidi, B. Gawdzik: Novel porous materials from lignin methacrylates copolymerized with St and DVB

13:15 - 14:30 Lunch

14:30 - 15:15 Working Group leader presentations 15:15 – 15:45 Overview of Action from the Chair

16:00 – 17:30 Management Committee meeting

17:30 End of workshop

17:30 - 18:30 Publication task group meeting

Keynote speakers:

Lars Berglund:

Mechanical behavior of nanocellulose-based materials

Olli Ikkala:

Functional nanocelluloses using self-assemblies and supramolecular interactions

Vincent Bulone:

Cell wall polysaccharides biosynthesis in eukaryotes and materials applications

Abstracts Session I:

EXTENSIBLE FIBRE NETWORKS FOR CELLULOSE-BASED

COMPOSITE MATERIALS

ALEXEY KHAKALOa, ALEXEY VISHTAL

b, ILARI FILPPONEN

a, ELIAS RETULAINEN

b, JANNE

LAINEa, ORLANDO J. ROJAS

a

aAALTO UNIVERSITY SCHOOL OF CHEMICAL TECHNOLOGY, DEPARTMENT OF FOREST

PRODUCTS TECHNOLOGY, P. O. BOX 16300, 00076 AALTO, FINLAND bVTT TECHNICAL RESEARCH CENTRE OF FINLAND, P.O. BOX 1603. KOIVURANNANTIE 1,

JYVÄSKYLÄ, 40101 FINLAND

ABSTRACT The use of cellulosic fibres as a reinforcing agent in composite materials has gained an increasing attention during the past few years. Typically, cellulose is used as a reinforcing agent in the composite matrix (Wang et al. 2015). However, in some applications besides providing stiffness, fibre networks should also contribute to the extensibility of the matrix. For instance, in thermoforming like processes for the preparation of cellulose-based materials with advanced 3D shapes cellulose so called formability is a crucial parameter (Vishtal et al. 2013). The term ‘‘formability’’ describes the ability of a material to undergo plastic deformation without damage and therefore it is highly associated with the extensibility. Moreover, the extent of fibrous fillers added to the composite is limited due to composites brittle behaviour once the filler loading has exceeded an optimal dosage. Therefore, increasing cellulose filler content without impairing the composites ductile properties might lead to lowering the manufacturing costs and, hence, represents an attractive route in preparation of biodegradable materials of various advanced 3D shapes with high cellulose content. In this work, high consistency fibre refining followed by subsequent low consistency treatment was employed to improve the stretch potential of a single fibre, degree of bonding between the fibres and to modify the fibre network. Optimization of refining process regarding the fibre properties was performed and the fibre networks made thereof were investigated with respect to their mechanical performance. Moreover, it was observed that the application of gelatin could even further increase the extensibility (formability) of the fibre network (Khakalo et al. 2014). Interactions between gelatin and cellulose were elucidated under different pH conditions with the help of surface sensitive tools such as quartz crystal microbalance with dissipation (QCM-D), surface plasmon resonance (SPR) and X-ray photoelectron spectroscopy (XPS). As a result, a 3D shape made of cellulosic fibres with improved extensibility was prepared (Fig. 1.).

Figure 1: Stamped unmodified (a) and gelatin-treated fibre networks (4 wt.% gelatin) (b). The dimensions of the formed shapes were approximately 110 mm (length) x 70 mm (width) x 35 mm (depth).

REFERENCES

Khakalo, A., Filpponen, I., Johansson, L.-S., Vishtal, A., Lokanathan, A.R., Rojas, O. J. and Laine, J.

(2014). Using gelatin protein to facilitate paper thermoformability. Reactive & Functional Polymers 85,175–

184.

Vishtal, A., Hauptmann, M., Zelm, R., Majschak, J-P. and Retulainen, E. (2013). 3D forming of

paperboard: the influence of paperboard properties on formability. Packag. Technol. Sci.; 27: 677–691.

Wang, S., Lin, Y., Zhang, X. and Lu, C. (2015). Towards mechanically robust cellulose fiber-reinforced polypropylene composites with strong interfacial interaction through dual modification. RSC Advances, 2015, 5, 50660.


FORMATION AND PROPERTIES OF NANOFIBRILLATED CELLULOSE BASED

COMPOSITES

IDA POLJANŠEKa , VESNA ŽEPIČ

b, PRIMOŽ OVEN

a

a University of Ljubljana, Biotechnical Faculty, Department of Wood Science and Technology,

Jamnikarjeva 101, SI-1000 Ljubljana, Slovenia. E-mail: [email protected] b TECOS, Slovenian Tool and Die Development Center, Kidričeva 25, SI-3000 Celje, Slovenia

ABSTRACT Nanocellulose has excellent mechanical properties and is therefore suitable to be used as a

reinforcing material in different composites. However, as for any nanoparticle, the main

challenge in formulation of composite is related to homogeneous dispersion within a polymer

and compatibility with the hydrophobic matrix. The aim of this presentation is to review research

work which was done in the field of nanocellulose based composites at University of Ljubljana in

recent years.

First part of the work was devoted to the development of biodegradable nanocomposites, based

on polylactic acid (PLA) and polyhydroxy butyrate (PHB) reinforced with nanofibrillated cellulose

(NFC). NFC used in these composites was neat or pre-treated by different drying procedures

(solvent exchange, drying in technical oven, freeze drying and spray drying) and thereafter

chemically modified. Acetylation reaction was employed for modification of NFC surface. PLA

films containing different amounts of unmodified and acetylated NFC were prepared by solution

casting. Whereas in the case of PHB, composites with different amounts of unmodified and

acetylated NFC were prepared by extrusion moulding technology. Second part of research

includes assembly and characterization of composites made of polyvinyl alcohol (PVA),

untreated NFC and bioactive compound obtained with extraction from heartwood and knots of

pines. Crude polar extract and isolated pinosylvin was used.

Selected properties of composites will be demonstrated, among them distribution of reinforcing

NFC within the matrices, thermal properties, mechanical properties, and fungicidal properties in

the case of PVA/NFC/bioactive compound composites.

mailto:[email protected]


HYDROPHOBIZATION OF NANOCELLULOSE-BASED WET-SPUN

FILAMENTS FOR HIGH PERFORMANCE MATERIALS

GISELA CUNHAa, MERI LUNDHAL

a, ORLANDO ROJAS

a,b

BIOBASED COLLOIDS AND MATERIALS GROUP (BICMAT), DEPARTMENT OF FOREST

PRODUCTS TECHNOLOGY, AALTO UNIVERSITY, SCHOOL OF CHEMICAL TECHNOLOGY,

P.O. BOX 16300, 00076 AALTO, FINLANDa

DEPARTMENT OF FOREST BIOMATERIALS AND CHEMICAL AND BIOMOLECULAR

ENGINEERING, NORTH CAROLINA STATE UNIVERSITY, CAMPUS BOX 8005, RALEIGH,

USAb

ABSTRACT

Natural polymers have been gaining tremendous momentum in the last years due to global

ecological and economical concerns. In particular, cellulose and its unique properties, have been

attracting the attention of many materials scientists and engineers devoted to the fabrication of

high performance materials deriving mainly from renewable resources. Cellulose nanofibrils are

recently being used to prepare strong cellulose filaments via different spinning techniques

(Håkansson et al. 2014, Hooshmand et al. 2015, Iwamoto et al. 2011, Walther et al. 2011).

However, the intrinsically high moisture sorption capacity of cellulose compromises the practical

application of such filaments, since their mechanical performance is lost, or significantly

diminished, once in contact with water or moisture. In order to overcome this drawback,

chemical modification can be applied to the surface of the nanocellulose-based filaments,

hindering their interaction with water molecules.

In the present work, we have adopted a simple chemical vapour deposition (CVD) approach to

hydrophobize nanocellulose-based wet-spun filaments using chlorosilanes.

Treatment with chlorosilanes resulted in hydrophobic filaments possessing interesting

morphological features. Thorough characterization is being conducted, but it is envisaged that

such filaments will have good compatibility with non-polar matrices for the preparation of

composite materials.

REFERENCES Håkansson, K.M.O., Fall, A.B., Lundell, F., Yu, S., Krywka, C., Roth, S.V., Santoro, G., Kvick, M., Wittberg, L.P., Wågberg, L. and Söderberg, D. (2014) Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments. Nature Communications 5:4018. Hooshmand, S., Aitomäki, Y., Norberg, N., Mathew, A.P. and Oksman, K. (2015) Dry spun single filament fibers comprising solely of cellulose nanofibers from bio-residue. Applied Materials & Interfaces DOI: 10.1021/acsami.5b03091. Iwamoto, S., Isogai, A. and Iwata, T. (2011) Structure and mechanical properties of wet-spun fibers made from natural cellulose nanofibers. Biomacromolecules, 12, 831-836. Walther, A., Timonen, J.V.I, Díez, I., Laukkanen, A. and Ikkala, O. (2011) Multifunctional high-performance biofibers based on wet-extrusion of renewable native cellulose nanofibrils. Advanced Materials, 23, 2924-2928.

Abstracts Session II:

CO-ASSEMBLY OF CELLULOSE NANOCRYSTALS AND HIGH ASPECT RATIO

NANOPARTICLES

Ahu Gümrah Dumanlı and Ullrich Steiner

Soft Matter Physics, Adolphe Merkle Institute, Chemin des Verdiers CH-1700 Fribourg Switzerland

ABSTRACT Self-assembly of cellulose nanocrystals (CNCs) dispersed in a chiral nematic phase, Figure 1 may enable

production of new composites with properties controlled by applying fields, changing temperature, and using

other external stimuli [1]. In this work, we develop CNC-based composites with chiral nematic order. In

particular, we describe the use of colloidal dispersions of CNCs as self-assembly directing agent for various

anisotropic nano particles including gold, silver and TiO2 nanorods with similar aspect ratios to CNCs.

In order to utilize these composites for development of various devices (sensors, light harversing systems,

diagnosis tools etc) investigating the morphology and the chemistry of the CNCs and various nanoparticles

with a selection of sizes and surface chemistry is of great importance. Therefore, we have developed a

technique to monitor the chiral nematic phase formation of the chiral nematic solid films through optical

microscopy (by analysing the circular dichroism) and SEM and my talk will be focusing on our latest findings

of these observations.

Figure 1 (a) Photograph of a CNC solid film (b) LCP microscopy image of the area marked on the petri dish

REFERENCES

1. Dumanli, A.G., G. Kamita, J. Landman, H. van der Kooij, B.J. Glover, J.J. Baumberg, U. Steiner, and S. Vignolini,

Controlled, Bio-inspired Self-Assembly of Cellulose-Based Chiral Reflectors. Advanced Optical Materials, 2014. 2(7): p.

646-650.


Cellulose nanofibers films reinforced with chitin nanocrystals for fungal inhibition

EDUARDO ROBLESa, ASIER M. SALABERRIA

a, RENE HERRERA

a, LUIS SERRANO

c, JALEL

LABIDIa, SUSANA C. M. FERNANDES

b

aBiorefinery Processes Research Group, Chemical & Environmental Engineering Department, University

of the Basque Country UPV/EHU, Plaza Europa 1. 20018. San Sebastian, Spain bDivision of Glycoscience, School Biotechnology, Royal Institute of Technology (KTH), AlbaNova

University Center, SE-10691 Stockholm, Sweden cLaboratoire de Génie des Procédés Papetiers (LGP2) Centre de Recherches sur les Macromolécules

Végétales (CERMAV-CNRS) Saint-Martin-d’Hères Cedex, France

ABSTRACT Cellulose and chitin, two main components of alimentary industry were obtained from blue agave

and yellow squat lobster by-products employing standard chemical methods. Cellulose

nanofibers were obtained by high pressure homogenization, while chitin nanocrystals were

hydrolyzed in acid medium to obtain nanocrystals as previously reported by this group

(Salaberria et al. 2014). The morphology of the cellulose nanofibers and chitin nanocrystals was

evaluated with X-Ray diffraction to observe crystallinity, Atomic Force Microscopy (Fig. 1) and

Dynamic Light Scattering were selected to evaluate the size of the particles and Infrared

spectroscopy (attenuated total reflectance) was used to evaluate the chemical composition of

the different materials. Seven different films (Table 1) were manufactured with standard hot

pressing method (Urruzola et al. 2013) and their properties were evaluated. Antifungal effect of

the chitin nanocrystals was studied; mechanical properties were measured with a MTS tensile

testing machine (Table 1) and surface tension with sessile drop contact angle method. The

addition of chitin nanocrystals enhanced mechanical properties of cellulose films. Presence of

chitin nanocrystals inhibited fungal growth.

Table 1: Code and composition for the different composites

Sample Cellulose

%

Chitin

%

0S 100 0

1S 99 1

3S 97.5 2.5

5S 95 5

7S 92.5 7.5

9S 91 9

10S 90 10

Figure 1: AFM images of a) 0S, b) 5S and c) 10 S, the increased presence of chitin nanocrystals can be clearly

observed.

The addition of particles with high crystallinity diminished the elongation of the papers but

increased the inner modulus. Behavior of the papers (Table 1) while varying the chitin content

presents a curious and unexpected result, as it goes from lesser UTS when content is 0 or 10

percent and has a better resistance when nanopaper has 2.5 or 7.5 wt% of chitin nanocrystals.

Table 1: Ultimate tensile stress (σ), strain (ε), Young modulus (E), Grammage (G) and porosity (P) of the

different films, number in parenthesis represents standard deviation in percent.

Sample σ

(MPa)

ε

(%)

E

(GPa)

G

Kg m-3

P

(%)

0S 56.63 (3) 7.57 (5) 2.73

(7)

94.53

31

1S 55.11(4) 3.91 (10) 3.02 (7) 77.51 23

3S 57.99 (3) 4.01 (9) 2.95 (4) 70.98 23

5S 55.42 (2) 3.22 (6) 2.87 (7) 70.11 25

7S 57.22 (1) 3.75 (9) 2.98 (4) 69.73 27

9S 57.19 (2) 3.81 (5) 3.19 (5) 78.52 21

10S 54.77 (2) 3.92 (6) 2.31 (2) 78.91 23

REFERENCES Salaberria A. M., Labidi, J., Herrera, R., Fernandes, S. C. M., (2014). Role of chitin nanocrystals and nanofibers on physical, mechanical and functional properties in thermoplastic starch films. Food Hydrocolloids, 46, 93-102. Urruzola, I., Robles, E., Serrano, L., Labidi, J., (2014). Nanopaper from almond (Prunus dulcis) shell. Cellulose 21(3), 1619-1629.

ACKNOWLEDGMENTS

The authors would like to acknowledge the European Commission through the project ECLIPSE

CP 280786 and Mexican Council of Science and Technology (CONACyT), through scholarship

No. 216178 for financially supporting this work. The authors thank for technical and human

support provided by SGIker of UPV/EHU for XRD, and AFM characterizations.


Bionanocomposite films from Resilin-CBD bound to

Cellulose nanocrystals

Amit Rivkin1, Tiffany Abitbol

1,2, Yuval Nevo

1, Ronen Verker

6, Shaul Lapidot

1, Anton Komarov

3,

Stephen C. Veldhuis3, Galit Zilberman

4, Meital Reches

5, Emily D. Cranston

2 and Oded Shoseyov

1

1The Hebrew University of Jerusalem, Faculty of Agriculture, Department of Biochemistry, Rehovot,

Israel. e-mail: [email protected] 2McMaster University, Department of Chemical Engineering, Hamilton, ON.

3McMaster University, Department of Mechanical Engineering, Hamilton, ON

4RD&E Division, Elbit Systems Electro-optics-Elop Ltd., Rehovot, Israel.

5The Hebrew University of Jerusalem, Institute of Chemistry, Givat Ram, Israel.

6Soreq NRC, Space Environment Department, Yavne, Israel

Keywords: Resilin-CBD, Cellulose nanocrystal, Nanocomposites.

ABSTRACT

This work explores the properties of bionanocomposite films prepared by binding recombinant

resilin-like protein (res), consisting of the exon 1 resilin sequence from Drosophila melanogaster

engineered to include a cellulose binding domain (CBD), to cellulose nanocrystals (CNCs). The

optimal binding of res-CBD to CNCs was 1:5 by mass, and the resulting res-CBD-CNCs

remained colloidally stable in water. Res-CBD-CNCs were solvent cast into transparent, free-

standing films, which were more hydrophobic compared to neat CNC films, with water contact

angles of 70-80°, compared to 35-40°. In contrast to the multi-domain orientation typical of chiral

nematic CNC films, res-CBD-CNC and CBD-CNC films exhibited long-range, uniaxial orientation

that was apparently driven by the CBD moiety. Glycerol was studied as an additive in the films in

order to determine whether the addition of a “wet” component to solvate the recombinant protein

improved the mechanical properties of the res-CBD-CNC films; in comparison to the other films,

res-CBD-CNC films were more elastic with added glycerol in the range of 0.5-5 wt. % (i.e,

responded more elastically to a given strain and/or were less plastically deformed by a given

mechanical load), but became less elastic when the glycerol loading was increased to 25 wt. %.

Overall, films made of res-CBD-CNCs plus 0.5 wt. % glycerol displayed improved mechanical

properties with an increase compared to neat CNC films in toughness of 150% (measured by

Instron) and elasticity of 100% (measured by DMA).

REFERENCES:

A. Rivkin, T. Abitbol, Y. Nevo, R. Verker, S. Lapidot, A. Komarov, S. C. Veldhuis, G. Zilberman, M. Reches, E. D. Cranston and O. Shoseyov. Industrial biotechnology. 2015 Feb, 11 (1): 44-58.

Abstracts Session III:

Wood and nanocellulose: deconstruction and assembly via multiphase systems

ORLANDO ROJAS

BIOBASED COLLOIDS AND MATERIALS GROUP (BICMAT), DEPARTMENT OF

FOREST PRODUCTS TECHNOLOGY, AALTO UNIVERSITY

ABSTRACT Cellulose nanofibrils (CNF) is a material containing fibrils with length in the micrometre and width

in the nanometre scales, forming a network structure. CNF can be prepared by its liberation from

the constituent fibre matrix and microfiber bundles. The nanofibrils contain both disordered and

crystalline cellulosic regions. This fibrillar material is differentiated from crystalline cellulose,

referred to as cellulose nanocrystals (CNC) or nanowhiskers. In this talk we will introduce novel

approaches to wood deconstruction for the development of both CNF and CNC. This is taking

advantage of the unique properties of liquid multiphase systems. They mainly consist of

microemulsions with super-solubilizing power and ultralow interfacial tension. Remarkably, the

same systems used in deconstruction will be employed in assembly: the cellulosic materials are

easily converted into fibres, films and particles. In this talk we will discuss main approaches and

principles used in these novel approximations to the valorisation of biomass


Strategies for the modification and functionalization of wood cell walls for the development of functional wood-polymer hybrid materials

Tobias Keplingera,b

, Etienne Cabanea,b

, Ingo Burgerta,b

Institute for Building Materials, Wood Materials Science, ETH Zurich, Switzerlanda

Applied Wood Materials Lab, Wood Materials Science, EMPA Dübendorf Switzerlandb

ABSTRACT

Wood is considered as one of the oldest building materials due to its wide availability and its

excellent mechanical properties which is a result of its unique hierarchical structure.

This hierarchical structural not only makes wood an ideal construction material but also offers

the possibility to use the wood scaffold for the synthesis of advanced hybrid materials for new

application fields e.g. in membrane/filtering technologies or as an energy storage material. To

use wood as a scaffold would be highly desirable as it still remains extremely challenging in

materials science to achieve bioinspired materials with the wood inherent micro/nanostructure

across multiple length scales.

In this respect recent developments of our research for the specific and controlled

functionalization of the wood structure with polymers will be presented.

By simply using methacryl group bearing precursors with different reactivity the distribution of the

methacryl groups within the wood cell wall can be controlled. This leads to the possibility of a

spatially controlled in situ polymerization as the methacryl groups are used as anchor points.

Furthermore new polymerization techniques for the incorporation of new functionalities, for

instance based on stimuli responsive


Hierarchical cellulosic bio scaffolds derived from wood using chemical delignification methods adapted from industry.

Jana Segmehla,b

, Tobias Keplingera,b

, Ingo Burgerta,b

Institute for Building Materials, Wood Materials Science, ETH Zurich, Switzerlanda

Applied Wood Materials Lab, Wood Materials Science, EMPA Dübendorf Switzerlandb

ABSTRACT In nature, combinations of different material classes, like polymers and minerals, are abundantly

used to achieve outstanding properties and multifunctionality. Herein not only the chemistry of

the chosen materials, but also their hierarchical arrangement and structure of the components

play a fundamental role.

From Pulp and Paper Industry several different chemical procedures for lignin removal of

mechanically disintegrated pulps are established. Adapting these methods to the treatment of

bulk wood allows us for an increased accessability of the structure down to the nanoscale, while

the hierarchical organization of the wood is still preserved.

A utilization of the prefabricated wood scaffold for the formation of nano-composite materials

was established through backfilling the newly developed free volume in the cell wall structure

with pre- synthesized, ultra-small fluorescent HfO2: Eu particles.

Spatially resolved Raman Spectroscopy and Electron Microscopy were used to monitor the self-

organization of the particles inside the cellulosic scaffold.

The analysis shows that structure coordinated assemblies of nanoparticles can be achieved,

which could reveal new aspects of the ultrastructural organization of wood. Further, variation of

the chosen nanoparticle system allows to target widespread applications for these novel bio-

based composite materials.

Session Poster Presentations:

SYNTHETIC AND MECHANICALLY IMPROVED CELL WALL MADE FROM NANO

CELLULOSE, LIGNIN AND RUBBER LIKE PROTEIN - RESILIN

Itan Preis1, Yiftach Birger

1 and Oded Shoseyov

1

1Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew University of Jerusalem,

Israel, Rehovot, Israel

Abstract

Resilin is a polymeric rubber-like protein, secreted by insects to specialized cuticle regions. Its

unique mechanical properties allow, among others, the outstanding jumping ability of fleas, up to

400 times their size. Resilin is attached to chitin, a polysaccharide and the main component of

the cuticle, via chitin binding domain. Polymerization of the protein is achieved by formation of

di-tyrosine bridges within resilin monomers in a free radical cross linking reaction.

This highly resilience and elastic protein was optimized for expression in tobacco and was

directed to the cell wall by a signal peptide. Cross-linking of resilin to the cell wall polyphenols

was enabled by utilizing the presence of natural plant cell wall peroxidases.

Here we attempted to mimic in vitro, the synthesis of the cell wall in transgenic plants, by mixing

crystalline nano cellulose (CNC), lignin and resilin in different concentrations, together with

horseradish peroxidase (HRP) and under oxidative conditions. Resilin was shown to cross link

with coniferyl alcohol by FTIR analysis. The mechanical properties of the polymer and the effect

of increasing concentration of resilin will be determined by nanoindentation. Cellulose binding to

the polymer is expected to occur via the cellulose binding domain (CBD) of the recombinant

resilin and will be tested by X-ray Diffraction (XRD).

We expected that the new cellulose-lignin-resilin biocomposite will help better understand the

integration of resilin to the plant cell wall. Moreover, such a novel polymer, that combines both

strength and elasticity, can be utilized in the future for different industrial applications.


STUDIES ON THE DIFFUSION ACROSSBACTERIAL CELLULOSE MEMBRANES

EZGI BAKIRCIa, MIGUEL GAMA

b

DEPARTMENT OF MATERIAL SCIENCE AND NANOENGINERING, SABANCI UNIVERSITYa

DEPARTMENT OF BIOLOGICAL ENGINEERING, UNIVERSITY 0F MINHOb

ABSTRACT

Cellulose is the most abundant bio-polymer on the earth and it has been used by humans for

many years. However, in the last 30 years, studies have focused on bacteria that can produce

cellulose. Bacterial cellulose is chemically pure, free of lignin and hemicellulose (there is no

need for chlorinechemical bleaching) and has high polymer crystallinity and high degree of

polymerization that distinguishes it from other forms of cellulose. The literature indicates that

bacterial cellulose is reliable and widely used in the food packaging industry and in biomedical

applications (Andrade, 2010).

According to the object of this study, bacterial cellulose was produced by using

Gluconacetobacterxylinus (ATCC 700178) cultures. Investigations of the biosynthesis, methods

of purification was reviewed and demonstrated by the results of current study. In the

experiments, dried bacterial cellulose membrane was drying at 60ºC overnight. They were

stored at room temperature in distilled water until using in experiment. The objective was to

determine the difference between the wet membranes and dry membrane and also determine

their diffusivities, characteristics and elucidate the mechanisms governing transport in relation to

the membrane structure. Diffusion cells were used for the diffusion tests. The diffusion

coefficients of polyethylene glycol (600, 900, 3350, 6000, 8000, 35000, 100000 Da) in the

bacterial cellulose membrane (wet and dry) were found by using the retention time method.

The results showed that bacterial cellulose membranes had high diffusivity rates for the tested

polyethylene glycols. As the molecule size of polyethylene glycols increased, the retention time

also increased in both bacterial cellulose membranes.The results show that the diffusivity of

polyethylene glycols in wet bacterial cellulose membranes was higher than that of dry bacterial

cellulose. The retention time in wet bacterial cellulose membranes is consistently longer than dry

membranes with the exception of polyethylene glycol 35,000 Da, polyethylene glycol 100,000

Da. The reason for this situation was probably that bacterial cellulose pore size became smaller

or membranes had few holes that covered with rough strings, when the bacterial cellulose

membranes dried.

REFERENCES

Andrade, F. K., R. A. N. Pértile, Dourado, F., Gama, F. M. P. (2010). BacterialCellulose: Properties, productionandapplications. Cellulose, Structure and Properties. Adam M. Sokolnicki, Robert J. Fisher, T. P. Harrah, D. L. Kaplan (2005). Permeability of Bacterial Cellulose Membranes. D. Klemm, D. Schumann, U. Udhardt, S. Marsch (2001). Bacterial Synthesized Cellulose — Artificial Blood Vessels for Microsurgery. S.R. Stephens, J.A. Westland, A.N. Neogi (1990). ‘’Method of usingbacterial cellulose as a dietary fiber component’’.


Current Methods for Cellulose Nanocrystals Preparation: Comparative and Critical Assessment

Jia Mao

a, b, Marie-Pierre Laborie

a,b

a Chair of Forest Biomaterials, Faculty of Environment and Natural Resources, University of Freiburg, Werthmannstr. 6, 79085 Freiburg, Germany b Freiburg Materials Research Center (FMF), University of Freiburg, Stefan-Meier Str. 21, 79104 Freiburg, Germany

ABSTRACT

Cellulose nanocrystals (CNCs) are mainly produced using a top-down approach from various

cellulosic materials. The extraction methods have significantly varied aiming at maximum CNC

yield and quality keeping in mind the environmental and economic aspects of production.

Recently, high yield-routes for the production of CNCs using ionic liquids have been developed

and optimized (Mao et al. 2013; Mao et al. 2015). This presentation will provide an overview on

the traditional strong acid hydrolysis approaches followed by a survey of the more recent and

sophisticated approaches. Meanwhile, the advantage and disadvantage of using ionic liquids for

the production of CNCs compared to other methods will be discussed via three parameters, which

are proposed to quantitatively assess the production efficiency and severity for various CNCs

production methods.

REFERENCES

1. Mao, J.; Heck, B.; Reiter, G.; Laborie, M-P. Cellulose nanocrystals’ production in near theoretical yields

by1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) – mediated hydrolysis. Carbohydrate

Polymers, 117, 443–451, 2015.

2. Mao, J.; Osorio-Madrazo, A.; Laborie, M-P. Preparation of cellulose I nanowhiskers with a mildly acidic

aqueous ionic liquid: reaction efficiency and whiskers attributes Cellulose, 20 (4): 1829–1840, 2013.

Acknowledgements

This project is funded by the EU European Funds for Regional Development and the

Department of Agriculture and Consumer Protection (MLR) of Baden-Württemberg, Germany.

Jia Mao acknowledges the PhD stipend from the Elisabeth und Barbara Grammel Foundation.


Protein separation using magnetically responsive cellulose nanocrystals

Jiaqi Guoa, Ilari Filpponen

a and Orlando J. Rojas

a

a Department of Forest Products Technology, School of Chemical Technology, Aalto University, 00076

Espoo, Finland

ABSTRACT Protein separation using a nanocomposite comprised of magnetite nanoparticles (NH2-Fe3O4)

embedded on the cellulose nanocrystals (CNC) is demonstrated. Magnetically responsive hybrid

CNCs were prepared as follows: Amino-functionalized superparamagnetic Fe3O4 synthesized

via co-precipitation methods (Mahmoud et al. 2013) were conjugated with TEMPO-oxidized

cellulose nanocrystals (TO-CNC) by covalent EDC/NHS coupling reaction (Filpponen et al.

2010). Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy

(XPS) were employed to investigate the structural and chemical characteristics of prepared

hybrid materials. Furthermore, the morphology of synthesized CNC hybrids was explored by

transmission electron microscopy (TEM). Finally, as prepared magnetically responsive CNC

hybrids were employed for the separation of a model protein lysozyme from a solution. Results

demonstrate the protein binding capacity and potential application of magnetically responsive

CNCs for protein separation.

REFERENCES

Filpponen, I., and Argyropoulos, D. (2010). Regular linking of cellulose nanocrystals via click chemistry: synthesis and formation of cellulose nanoplatelet gels. Biomacromolecules, 11 (4), 1060–1066 Mahmoud, K., Lam, E., Hrapovic, S., and Luong, J. (2013) Preparation of well-dispersed gold/magnetite

nanoparticles embedded on cellulose nanocrystals for efficient immobilization of papain enzyme. ACS

Applied Materials&Interfaces, 5 (11), 4978–4985


Hybrid Thin Films from ZnO and Nanocellulose

Hua Jin, Benjamin Wilson, Eero Kontturi, Tekla Tammelin, Maarit Karppinen

Aalto University, Kemistintie 1, FI-02150 Espoo, Finland, E-mail: [email protected]

ABSTRACT In this work, we fabricated hybrid superlattice thin films from ZnO and nanocellulose (NC) to tune

properties of ZnO films [1, 2]. The ZnO layers were deposited by atomic layer deposition (ALD)

and NC layers were from dip coating. By controlling the ALD processes and dip coaing

processes, the thickness of ZnO and NC layers and thereby the transport properties (Seebeck,

electrical resistivity, and thermal conductivity) can be controlled. Annealing under different

atmospheres was carried out to investigate stability of the superlattice structurs. X-ray reflectivity

(XRR) was used to determine the thickness of hybrid films and nanoindentation to investigate

mechanical properties

Figure 1: Optical photos and XRR spectra of hybrid films with 100 cycles of ZnO and one layer of NC as

repeating units

REFERENCES Tynell, T., Karppinen. M., (2014), ZnO: Hydroquinone superlattice structures fabricated by ALD/MLD. Thin solid films, 551, 23-26 Tynell, T., Giri, A., Gaskins, J., Hopkins, P.E., Mele, P., Miyazaki, K., Karppinen, M., (2014), Thermoelectric Characteristics of (Zn, Al)O/hydroquinone superlattices. J. Mater. Chem. A, 43 (1), 13619-13624


PHASE BEHAVIOR AND MISCIBILITY IN ALL-LIGNOCELLULOSIC POLYMER BLEND SYSTEMS

GLEUWITZ, R.,

a,b FRIEDRICH, C.,

b LABORIE, M.-P.,

a

a CHAIR OF FOREST BIOMATERIALS, ALBERT LUDWIG UNIVERSITY OF FREIBURG, 79085

FREIBURG, GERMANY b FREIBURG MATERIALS RESEARCH CENTER, ALBERT LUDWIG UNIVERSITY OF FREIBURG,

79085 FREIBURG, GERMANY

ABSTRACT This project aims at developing novel polymer blends consisting of lignin and a cellulose

derivative with tunable rheological properties. Here a high lignin content and adequate

processability under high shear rates, both relevant to 3D printing processes, are required. In

this regard, the approach pioneered by Rials and Glasser (Rials and Glasser 1989, 1990) on

blending lignin with liquid crystalline cellulosic derivatives is pursued. Within this particular study

the miscibility of the polymers and the morphology of the blends are investigated. Our approach

initially consists of analysis on the solution scale by polarized light microscopy and light

scattering and further on the bulk scale by differential scanning calorimetry.

In this presentation, preliminary results regarding the polymer solution will be discussed.

Turbidity measurements are conducted to detect the widely investigated LCST behavior of the

cellulosic polymer in water (Fortin and Charlet 1989; Schild and Tirrell 1990; Suto and Iwasawa

1993). Furthermore, the influence of the composition of the aqueous solvent system will be

investigated during the course of blending the lignocellulosic components. Variations regarding

the solvent system affect the hydrogen bonding and hydrophobic interactions (Fortin and Charlet

1989; Vshivkov 2011). Since the phase separation is of entropic origin, this in turn impacts the

LCST behavior, the chain dimensions and the tendency towards mesophase formation.

Accordingly we intend to analyze the self-assembly and the self-association of the polymer in

aqueous solutions by polarized light microscopy and by static and dynamic light scattering,

respectively.

This work is supported by a grant from the Ministry of Science, Research and the Arts of Baden-Württemberg to M.-P. Laborie

REFERENCES

Vshivkov, S.A. (2011) Effect of Magnetic and Mechanical Fields on Phase Liquid Crystalline Transitions in Solutions of Cellulose Derivatives. In: Thermodynamics - Physical Chemistry of Aqueous Systems. Ed. Moreno-Piraján, J.C. InTech. pp. 407–434.

Suto, S., Iwasawa, I. (1993) Liquid crystal-forming aqueous hydroxypropyl cellulose solutions: Effects of surfactants on the turbidity and shear viscosity. J. Polym. Sci. A Polym. Chem. 31:1599–1607.

Schild, H.G., Tirrell, D.A. (1990) Microcalorimetric detection of lower critical solution temperatures in aqueous polymer solutions. J. Phys. Chem. 94:4352–4356.

Rials, T.G., Glasser, W.G. (1990) Multiphase materials with lignin: 5. Effect of lignin structure on hydroxypropyl cellulose blend morphology. Polymer 31:1333–1338.

Rials, T.G., Glasser, W.G. (1989) Multiphase materials with lignin.: 4. Blends of hydroxypropyl cellulose with lignin. J. Appl. Polym. Sci. 37:2399–2415.

Fortin, S., Charlet, G. (1989) Phase diagram of aqueous solutions of (hydroxypropyl)cellulose. Macromolecules 22:2286–2292.


ALIGNMENT OF CELLULOSE NANOCRYSTALS INTO OAT SPELT

ARABINOXYLAN FILMS

TIAGO DOS SANTOS, HEIKO WINTER, MARIE-PIERRE LABORIE

UNIVERSITY OF FREIBURG, CHAIR OF FOREST BIOMATERIALS, WERTHMANNSTRASSE 6, 79085 FREIBURG, GERMANYa

ABSTRACT Oat spelt arabinoxylan (osAX) has been studied for several different applications as gel forming,

thermoplastic material, plastic films and others (Saake et al. 2006). Cellulose nanocrystals

(CNCs) have been largely explored due to their remarkable properties. In this work, osAX film is

reinforced with CNCs and the alignment of the CNCs is controlled. By a fixed spreading direction

of the mixture and the concentration of such mixture.

Fig. 1 shows the phase AFM images of the films and its alignment according to the variation in

concentration.

Figure 1: AFM phase images (2X2 μm) of the films a) osAX/CNCs 0.4 wt%, b) osAX/CNCs 0.4 wt%/Sorbitol

10 wt%, c) osAX/CNCs 3 wt%, d) osAX/CNCs 3 wt%/Sorbitol 10 wt%.

The AFM images were processed by a matlab code in order to determine the degree of

alignment. This method was already described by Hoeger et al. 2011 to determine degree of

alignment of pure CNCs. The matlab code used AFM topography images by performing a grain

partition and filtering the sizes of the grains. The angles of leading edge or the long axis of the

CNCs were determined in a polar plot between 0 and 90° with respect to the withdrawal

direction and the degree of CNC alignment was defined as the number % of CNCs in the angle

range between 0 and 20° in the withdrawal direction. According to the method, more than 300

CNCs were counted in each image analysis and at least 3 different locations, from 3 different

films, were analysed for each condition.

After the matlab code verification, it was found out higher concentration of CNCs lead to higher

alignment, while the sorbitol seems to have a small negative effect on the alignment, which

could be explained by the high affinity of sorbitol to the surface of the CNCs due to the high

amount of hydroxyl groups in both components. These results are summarized at the Table 1.

This might be because of the rod-like shape of the CNCs that can induce each other to move

towards the spreading direction of the liquid mixture before film formation. The samples with 0.4

wt% had regions of higher alignment but this was not as homogeneous as it was in the samples

with 3 wt%. This can be related to the low amount of CNCs and the influence of sorbitol, which

has interactions with the surface of the nanocrystals.

Acknowledgement The author thanks the program “Ciência sem Fronteiras – CNPq/Brazil” for the scholarship. The authors thank Prof. Dr. Bodo Saake (University of Hamburg) for the supply of osAX.

REFERENCES

Hoeger, I., Rojas, O.J., Efimenko, K., Velev, O.D., Kelley, S.S. (2011). Ultrathin film coatings of aligned cellulose nanocrystals from a convective-shear assembly system and their surface mechanical properties. Soft Matter, 7, 1957-1967. Saake, B., Erasmy, N., Kruse, T., Schmekal, E., Puls, J. (2003). Isolation and Characterization of

Arabinoxylan from Oat Spelts. In P. Gatenholm & M. Tenkanen (Eds.), Hemicelluloses: Science and

Technology (pp.52-65). Washington, DC: ACS Symposium Series.


Foam Forming with Cellulosic Fibers

Wenchao Xiang

a, Kristian Salminen

b, Timo Lappalainen

b, Erkki Saharinen

b, Ilari

Filpponena, Orlando J. Rojas

a

Bio-based Colloids and Materials (BiCMat) Group, Department of Forest Products Technology, Aalto University, Finland

a

VTT Technical Research Centre of Finland, Finlandb

ABSTRACT Foam is used as a medium in several applications such as in oil recovery, food industry, water

treatment, packaging, textile products, etc. Current environmental concerns have prompted an

increasing demand for bio-based materials in the production of foams. For example, cellulosic

foams are potential candidates to substitute water as suspending medium in papermaking

(Radvan and Gatward, 1972; Smith et al. 1974). This can result in remarkable reduced water

and energy consumption.

Foam forming is a complex process involving various colloidal interactions. Fundamental

understanding of the physicochemical interactions taking place at the interface between air

bubbles and aqueous phase still remains a challenge. In order to investigate the impact of

related mechanisms and interactions in foam forming, fiber aqueous dispersion and foams were

formulated with various surfactants to produce the corresponding handsheets. Mechanical

properties of foam-formulated handsheets were compared to handsheets produced from

aqueous dispersions. Foam dynamics (foamability and foam stability) of surfactants in the

presence of fibers were also studied.

Our results indicate that the nature of the fiber and type of surfactant used strongly affect the

mechanical properties of the foam-formulated handsheets. Results from foam dynamics studies

will contribute in our understanding of the physicochemical interactions (electrostatic, steric, etc.)

occurring at the interface of fibers and surfactants.

REFERENCES

Radvan B. and Gatward A.P.J. (1972). The formation of wet-laid webs by a foaming process. Tappi, 55 (5), 748-751. Smith M.K., Punton V.W., and Rixson A.G. (1974). The structure and properties of paper formed by a foaming process. Tappi, 57 (1), 107-111.


ESTER OF POLYOL AND TEMPO MODIFIED CELLULOSE: PREPARATION AND CHARACTERIZATION

JAKA LEVANIČ, PRIMOŽ OVEN, IDA POLJANŠEK

University of Ljubljana, Biotechnical faculty, Depratment of wood science and technology, Jamnikarjeva 101, 1000 Ljubljana, Slovenia. E-mail: [email protected]

ABSTRACT

Cellulose is the most abundant naturally occurring polymer, hence it is a prime candidate for the

development of innovative materials for use in different areas. Its chemical structure allows

modifications of its surface and hence preparation of more reactive form of cellulose for further

chemical processing (Khalil et al. 2014). TEMPO oxidized cellulose provides a raw material for

carrying out a number of chemical reactions including esterification. The goal of this research

was development of a castable resin, based on TEMPO oxidized cellulose and commercially

available polyols, which would have good mechanical properties.

TEMPO cellulose was prepared according to the TEMPO/NaClO/NaBr procedure developed by

Isogai et al (2011). A 5 gram sample of cellulose was grounded in a water cooled mill and

suspended in 250ml of distilled water. After soaking and stirring the cellulose for 24 hours it was

transferred into a 1000ml two neck reactor. The required amount of chemicals for the TEMPO

oxidation and distilled water were added to the cellulose suspension and the reaction was

carried out over a course of 1 hour under constant stirring at 500 rpm. The oxidized product was

filtered out and suspended in distilled water. Thereafter, mechanical disintegration with

Ultraturax and ultrasonic probe followed resulting in TEMPO cellulose gel. The product was

freeze dried and suspended in dichloromethane (DCM) for further processing. Amount of polyol

was calculated based on the theoretical values presented by Isogai et al (2011). Amount of other

reagents such as DPTS and DCC were calculated on the amount of available carboxylic groups

in TEMPO cellulose. Esterification was carried out at room temperature and constant stirring for

24 hours. The final product was filtered and washed with a small amount of cold DCM and dried

under a vacuum to obtain solid residue. The final product was analysed with FT – IR.

Dry ester looks like a solid and brittle mass when dried in a vacuum at room temperature; while

freeze dried ester was slightly foamy and more elastic than dry TEMPO cellulose.


Figure 1 IR spectra comparison between TEMPO modified cellulose (in blue) and the ester of polyol and TEMPO cellulose (in red)

IR spectra (Figure 1) shows the concentration of carboxylic groups (1605 cm-1) in ester of polyol

and TEMPO cellulose slightly decreased in comparison to TEMPO cellulose. On the other hand,

a new peak around 1650 cm-1 which belongs to an ester functional group occurred in spectrum

of ester of polyol and TEMPO cellulose. Further analyses of thermal properties of ester of polyol

and TEMPO cellulose showed lower decomposition temperature than that of pure cellulose and

TEMPO oxidized cellulose.

REFERENCES Khalil, H.P.S.A., Davoudpour, Y., Islam, N., Mustapha, A., Sudesh, K., Dungani, R., Jawaid, M. (2014). Production and modification of nanofibrillated cellulose using various mechanical processes: Carbohydrate Polymers, 99, 649– 665 Isogai, A., Saito, T., Fukuzumi, H. (2011). TEMPO-oxidized cellulose nanofibers. Nanoscale, 3(1), 71-85.


CELLULOSE-BASED NITROGEN DOPED CARBON AS OXYGEN REDUCTION REACTION CATALYST FOR FUEL CELLS

MARYAM BORGHEI

a, ELO KIBENA

b, LEENA-SISKO JOHANSSON

a, JOSEPH CAMPBELL

a, ESKO

KAUPPINEN c, KAIDO TAMMEVESKI

b, ORLANDO ROJAS

a

BIO-BASED COLLOIDS AND MATERIALS (BiCMat), DEPARTMENT OF FOREST PRODUCTS TECHNOLOGY, AALTO UNIVERSITY, FINLAND

a

INSTITUTE OF CHEMISTRY, UNIVERSITY OF TARTU, ESTONIA b

NANOMATERIALS GROUP, DEPARTMENT OF APPLIED PHYSICS, AALTO UNIVERSITY, FINLAND c

ABSTRACT Fuel cells (FCs) have become promising alternatives as sustainable energy conversion systems

over the last few decades. These devices involve electrocatalytic oxidation of a fuel (e.g.

hydrogen or alcohol) at the anode and oxygen reduction reaction (ORR) at the cathode.

However, commercialization of FCs has been limited due to the use of expensive Pt-based

eletrocatalysts.

In response to this challenge, a series of non-precious metal based ORR catalysts were

developed as alternatives to Pt. In addition, doping carbon nanomaterials such as carbon

nanotubes (CNTs) (Borghei et al. 2014) and graphene (Borghei et al. 2014) with nitrogen atoms

has shown significant electrocatalytic activity for ORR. However, synthesis of N-doped carbon

nanomaterials have been achieved under harsh reaction conditions, using expensive and rather

poisonous chemicals. In this regard, natural alternatives such as cellulose materials can be more

eco-friendly and economical alternatives to decrease the cost and improve the sustainability

aspects of the electrocatalysts based on natural/renewable resources (Liu et al. 2015).

In this study, nanofibrillated cellulose (NFC) and TEMPO-oxidized NFC were used to prepare N-

doped carbon for ORR. This has been done via a facile and low cost method by pyrolyzing

cellulose in the presence of nitrogen precursors such as polyaniline and dicyandiamide. The N-

doped carbon materials were characterized by Raman spectroscopy, Brouner-Emmet-Teller

(BET), scanning electron microscopy and X-ray photoelectron spectroscopy (XPS). The

characterization shows a porous and crystalline structure with successful incorporation of

nitrogen atoms. The ORR activity was studied using a glassy carbon electrode modified with

cellulose-based N-doped carbon, employing rotating disk electrode (RDE) method. The RDE

results indicated that these novel materials provide remarkable electrocatalytic activity toward

ORR.

REFERENCES Borghei, M., Kanninen, P., Lundahl, M. Susi, T., Sainio, J., Anoshkin, I., Nasibulin, A., Kallio, T., Tammeveski, K., Kauppinen, E., and Ruiz, V. (2014). High oxygen reduction reaction activity of few-walled carbon nanotubes with low nitrogen content, 158-159, 233-241. Borghei, M., Azcune, I., Carrasco, P., Sainio, J., Kauppinen, E., Ruiz, V. (2014) Nitrogen-doped graphene with enhanced oxygen reduction activity produced by pyrolysis of graphene functionalized with imidazole derivatives, 39, 12749-12756. Liu, Q., Chen, C., Pan, F., Zhang, J. (2015). Highly efficient oxygen reduction on porous nitrogen-doped nanocarbons directly synthesized from cellulose nanocrystals and urea, 170, 234-241.


Effect of processing parameters on the rheological behavior and morphology of microfibrillated cellulose

Hesam Taheri1, 2, 3

*, Marie-Pierre Laborie2, Pieter Samyn

1, 2

1University of Freiburg, Freiburg Institute for Advanced Studies, Faculty of Environment and Natural Resources, Chair for Bio-based Materials Engineering, Habsburgerstrasse 49, 79104 Freiburg, Germany 2Freiburg Materials Research Center, Stefan-Meier-Straße 21, 79104 Freiburg, Germany

3University of Freiburg, Hermann Staudinger Graduate School, Hebelstraße 27, 79104 Freiburg, Germany

*Corresponding author: [email protected],

Tel +49 761 203 97202 Fax +49 761 203 3675

Abstract

The rheological behaviors of microfibrillated cellulose (MFC)/nanofibrillated cellulose (NFC)

dispersions play an important role while it uses as a reinforcement into the polymer matrices.

Different parameters within the processing of MFC dispersion affect the rheological behaviors

such as viscosity, creep, strain recovery and yield stress of dispersion. In this work, the type of

chamber and number of passes within microfluidizer apparatus were investigated with two

parametrical elements, therefore, the main focus of this study relies on the rheological features

and morphological alterations of MFC dispersions due to different processing protocols. The

combination of morphological and rheological data is helpful to control further processing of MFC

dispersion. Moreover, these data is vital to optimize the fiber diameter and viscosity of MFC

dispersion due to the type of chamber and number of passes. The flocculation of MFC

dispersion over shear rate is a conventional barrier, which can be detected by rheometry

technique. Thus, the processing of MFC dispersion with an optimized fiber diameter and high

stability (non-aggregation) can be feasible with use of microscopy and rheometry. In this work,

the creep responses and the yield stress of MFC dispersions have been thoroughly studied with

use of the Burger model and Herschel-Bulkley model, respectively. The noteworthy observation

of this work is an intermediate recovery response, which shows step strain recovery. This

demonstrates that the MFC dispersions with high degree of fibrillation behave nor as MFC

dispersions neither as nanowhisker dispersions. Therefore, the novel term of

"quasinanocrystaline" has been proposed in this study.

REFERENCES

Rheometry, Shear rate, Viscosity, Creep, Microfibrillated cellulose


Session III continued:

NANOFIBRILLATED CELLULOSE AS ADDITIVE FOR WOOD COATINGS

FRANZISKA GRÜNEBERGER

a, TINA KÜNNIGER

a, ANJA HUCH

a, MARTIN ARNOLD

a, INGO

BURGERTa,b

, TANJA ZIMMERMANNa

a EMPA, APPLIED WOOD MATERIALS, UEBERLANDSTRASSE 129, 8600 DÜBENDORF,

SWITZERLAND b ETH ZÜRICH, INSTITUTE FOR BUILDING MATERIALS, WOOD MATERIALS SCIENCE 8093

ZÜRICH, SWITZERLAND

ABSTRACT Wood is a popular building material regularly used in exterior applications, where it is subjected

to UV radiation, rain, humidity, mechanical impacts and microorganisms. These impacts

adversely affect the natural appearance of wood and for this reason, wood surfaces are

protected by wood coatings, for which nanofibrillated cellulose (NFC) could act as novel,

bio‐based additive. NFC can be a multifunctional coating additive, which on the one hand can

act as carrier for functional, wood protective compounds and on the other hand influences the

physical properties of the coating.

Within a first feasibility study, NFC was processed with different waterborne polymeric binder

emulsions. Properties of liquid polymer-NFC suspensions and dry composite films were

examined with regard to the coating application. The viscosity of polymer-NFC suspensions was

measured depending on the NFC concentration and type of polymer emulsion. Furthermore, free

composite films were prepared from polymer-NFC suspensions and mechanical properties were

determined by tensile tests before and after composite film aging under artificial weathering

conditions.

NFC was further functionalized with two different model compounds, which are both commonly

utilized as UV protecting agents: inorganic zinc oxide (ZnO) nanoparticles and an organic UV

absorber (UVA). The functionalized NFC was afterwards compounded with one or two acrylic

coating binders. Free films as well as coated wood specimens were prepared and analysed.

Moreover, the coated wood specimens were artificially weathered. The presentation gives an

overview on the main results of this study, which was examined within a PhD thesis.

REFERENCES Grüneberger, F. Künniger, T., Zimmermann, T., Arnold, M. (2014). Rheology of nanofibrillated cellulose/acrylate systems for coating applications. Cellulose, 21, 1313–1326 Grüneberger, F. Künniger, T., Zimmermann, T., Arnold, M. (2014). Nanofibrillated cellulose in wood coatings: mechanical properties of free composite films. Journal of Materials Science, 49, 6437-6448 Grüneberger, F. Künniger, T., Huch, A., Zimmermann, T., Arnold, M. (2015). Nanofibrillated cellulose in wood coatings: Dispersion and stabilization of ZnO as UV absorber. Progress in Organic Coatings, 87, 112-121.


SUSTAINABLE SURFACE MODIFICATION OF WOOD

ALINA LOZHECHNIKOVA, MONIKA ÖSTERBERG

DEPARTMENT OF FOREST PRODUCTS TECHNOLOGY, SCHOOL OF CHEMICAL TECHNOLOGY, AALTO UNIVERSITY, FINLAND

ABSTRACT

Renewability, strength, visual appearance and good thermal insulation properties made timber

the material of choice for many applications, including building construction and furniture

manufacture. However, it is quite often required to fine-tune the properties of wooden material

for specific application. Conventional wood modification techniques are often not sustainable, as

they sometimes utilise toxic materials, organic solvents or potentially dangerous nanoparticles,

which can leak to nature. There are also methods using natural oils and waxes on the market

but these methods are based on impregnation and/or film formation on the wood surface and,

therefore, they reduce the natural moisture buffering ability of wood. Current work is focused on

the development of novel surface treatment for wood, exploiting the combination of hierarchical

roughness of the wooden surface with low surface energy of natural wax. Resulting surface is

less sensitive to liquid water while the natural ability of wood to release and absorb water vapour

is preserved. Intact buffering ability is important, as it can help to even-out large fluctuations in

relative humidity and ambient temperature. Consequently, this could result in reduced need for

mechanical ventilation, reduced energy consumption and improved energy efficiency of the

building in addition to increased comfort of living.

The surface hydrophobation of spruce is done utilizing wax microparticles instead of

conventional continuous films. The susceptibility of wooden surfaces to water before and after

the treatment was studied using contact angle measurements on radially and tangentially cut

samples. The ability of the wood to exchange moisture with the surrounding environment was

analysed during high and low humidity cycles, and quantified through the Moisture Buffer Value

(MBV) (Rode 2005). MBV of the treated wood was found to be between 1.0 -1.2, which is of the

same level as MBV of unmodified wood. It can be concluded, that the developed treatment

preserves good level of moisture buffering of spruce, while increasing the hydrophobicity of

surface.

REFERENCES Rode, C. (2005). Moisture buffering of building materials. BYG DTU-126 Report, Department of Civil Engineering, Technical University of Denmark, 2005, http://orbit.dtu.dk/fedora/objects/orbit:75984/datastreams/file_2415500/content


Wood meets art

Ling Wanga, Julio Arboledaa, Pirjo Kääriäinenb, Tapani Vuorinena, Orlando Rojasa,c

BIOBASED COLLOIDS AND MATERIALS GROUP (BICMAT), DEPARTMENTOF FOREST PRODUCTS

TECHNOLOGY, AALTO UNIVERSITY, SCHOOL OF CHEMICAL TECHNOLOGY, P.O. BOX 16300, 00076

AALTO, FINLANDa

DEPARTMENT OF ART DESIGN AND ARCHITECTURE, AALTO UNIVERSITY, HÄMEENTIE 135 C

HELSINKI, PB 31000, 00076 AALTOb

DEPARTMENT OF FOREST BIOMATERIALS AND CHEMICAL AND BIOMOLECULAR ENGINEERING,

NORTH CAROLINA STATE UNIVERSITY, CAMPUS BOX 8005, RALEIGH, USAc

ABSTRACT We report on recent projects that bring together two distinct area – Chemical Technology and

Art, Design and Architecture to produce cellulosic materials aiming at inspiring students and

researchers to explore biomaterials and to create new platforms to connect the properties of

wood with societal trends. Three prototypes - jacket, scarf and shoe concepts were developed

by combining cellulose based materials (aerogels, films, papers). The aerogels (Figure 1) made

from different types of cellulose and conditions were dyed with natural compounds and made

into shoe soles and scarf. The jackets was made from microcellulose papers and films from both

carboxymethylated and bacterial cellulose (Figure 1). The presentation will highlight not only the

design and creative process but the important influence of material properties in the

development of the materials. The assembly process and hierarchical arrangement of

nanocellulose will be factored as critical phenomena to bridge the form and performance

demands.

Figure 1. Aerogels and bacterial cellulose made under different conditions to develop new materials with impact to art and design.

Session IV:

Functional Materials from Nanocellulose

Hua Jin, Robin H.A. Ras, Olli Ikkala

Aalto University, Puumiehenkuja 2, FI-02150 Espoo, Finland, E-mail: [email protected]

ABSTRACT We show the vapour-driven Marangoni effect as a new paradigm for the continuous self-

propulsion of floating soft machines by transduction of chemical energy to motility, featuring a

prolonged locomotion at steady velocity with a small amount of on-board fuel. The propulsion is

induced by modification of the liquid surface using organic vapour transported through a

nanocellulose aerogel membrane. The steady velocity is achieved through a continuous supply

of fuel vapour that lowers the surface tension of the liquid, combined with the spontaneous

recovery of the surface tension after the floating machine has passed. The membranes are gas

permeable from their open-porous nanofibrillar structure and float on water and oils due to their

superhydrophobic and superoleophobic nature. The velocity is tunable by selecting solvents with

different vapour pressure.

Figure 1: Scheme for self-propulsion of a membrane driven by vapour and locomotion of an aerogel

REFERENCES Jin, H., Marmur, A., Ikkala, O., and Ras, R.H.A., (2012), Vapour-driven marangoni propulsion: continuous, prolonged and tunable motion. Chemical Science, 3, 2526 Jin, H., Kettunen, M., Laiho, A., Pynnonen, H., Paltakari, J., Marmur, A., Ikkala, O., and Ras, R.H.A., (2011), Superhydrophobic and superoleophobic nanocellulose aerogel membranes as bioinspired cargo carriers on water and oil. Langmuir, 27(5), 1930-1934

Session IV:

NOVEL IONIC LIQUID-MEDIATED PRODUCTION OF CELLULOSE NANOCERYSTALS DIRECTLY FROM WOOD

HATEM ABUSHAMMALA

a,c, INGO KROSSING

b,c, MARIE-PIERRE LABORIE

a,c

a CHAIR OF FOREST BIOMATERIALS, UNIVERSITY OF FREIBURG, WERTHMANNSTR. 6,

79085 FREIBURG, GERMANY b INSTITUTE OF INORGANIC AND ANALYTICAL CHEMISTRY, UNIVERSITY OF FREIBURG,

ALBERTSTR. 21, 79104 FREIBURG, GERMANY c

FREIBURG MATERIALS RESEARCH CENTER, UNIVERSITY OF FREIBURG, STEFAN-

MEIER-STR. 21, 79104 FREIBURG, GERMANY

ABSTRACT Cellulose Nanocrystals (CNCs) are traditionally produced using strong acid-catalyzed hydrolysis

of cellulosic sources. Such severe route generally requires pure forms of cellulose as a starting

material, such as pulp and microcrystalline cellulose, while no reports exist about the extraction

of CNCs directly from lignocelluloses such as wood. Therefore, mild and direct CNC production

routes from wood are needed. Ionic liquids (ILs) have shown a great potential for wood

dissolution, processing, and fractionation. They are often qualified as “green solvents” because

of their recyclability and reusability. More importantly, their dissolution affinities to wood

polymers can be tailored by varying their constitutive ions and the applied dissolution conditions

(temperature and time). In optimized conditions, ILs might be particularly suited for simultaneous

wood pulping and nanocellulose extraction. This presentation discusses the first report about the

extraction of CNCs directly from wood. The performance aspects of wood pulping and CNC

extraction and the properties of the produced CNCs are covered in addition to the overall

process optimization.

Session IV:

CHARACTERIZATION OF PORE SIZE DISTRIBUTION IN NANOFIBRILLATED CELLULOSE-BASED MEMBRANES: ASSESSMENT OF TWO POROSIMETRY

TECHNIQUES

P. ORSOLINIa,b

, P. TINGAUTa, T. ZIMMERMMANN

a, W. R. CASERI

b

aEMPA, Swiss Federal Laboratories for Materials Science and Technology, Applied Wood Materials

Laboratory, CH-8600 Dübendorf b ETH-Zürich, Multifunctional Materials, CH-8093 Zürich

ABSTRACT The need of substituting oil-based materials has also reached the field of separation processes.

A promising material for realizing sustainable membranes is Nanofibrillated Cellulose (NFC).

However, the characterization of the pore size distribution (PSD) inside such membranes

remains challenging. In the present study, we elaborated NFC membranes and focused on their

characterization. While gas adsorption techniques are devoted to the investigation of

membranes in their dry state, thermoporometry is a well-established method for studying porous

materials in their wet state. Consequently, thermoporometry seems to be the most convenient

tool to characterize water-filtration membranes. The advantage of such a system stems from the

use of water as probe liquid for pores, which suits well to hydrophilic materials such as cellulose.

In our work, the influence of the swelling time on the PSD of the swollen membranes has been

particularly investigated (Fig. 1). First results showed that thermoporometry is a rather reliable

method to characterize the PSD of NFC-based membranes in the mesoporous range: PSD

above a few nm in radius have been detected, however the upper distribution limit could not be

evaluated properly since the shift of water melting temperature was negligible for pore sizes

above 60 nm. Evidences confirm that both methods, gas adsorption and thermoporometry, are

unable to characterize macropores and generate PSD that differ extensively.

Figure 1: PSD derived from thermoporometry for NFC membranes depending on different swelling times.

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

0 10 20 30 40 50 60 70 80Rel

ativ

e p

ore

vo

lum

e (m

m3/g

)

Pore diameter - Medium pore (nm)

Pore size distribution of NFC membranes

Mem 5 hours

Mem 24 hours

Mem 200 hours

Session V:

On the Nanostructuring Role of Cellulose Nanocrystals on Maleic Anhydride Plasma Polymer Films

M.-P. LABORIE

a,b, M. BRIOUDE

a,b, H. HAIDARA

c, L. VONNA

c , V. ROUCOULES

c

a Chair of Forest Biomaterials, Faculty of Environment and Natural Resources, University of Freiburg, Werthmannstr. 6, 79085 Freiburg, Germany b Freiburg Materials Research Center (FMF), University of Freiburg, Stefan-Meier Str. 21, 79104 Freiburg, Germany c Institut de Science de Matériaux de Mulhouse CNRS UMR7361, Université de Haute-Alsace, 15 rue Jean Starcky, PB 2488, 68057 Mulhouse Cedex, France

ABSTRACT

Cellulose Nanocrystals (CNC) have been proposed to destabilize maleic anhydride plasma

polymer (MAPP) thin films resulting in microstructured wrinkled films by virtue of buckling

mechanics1. MAPP alone, viz. in the absence of nanocellulose, can also develop into microscale

and nanoscale structured thin films2, generating beads, needle-like and branched nano-

structures. These observations pose the question of whether CNCs enhance structuration in

MAPP films and if so whether this effect arises from a pure destabilizing effect or from a

nucleating mechanism. To answer these questions pulse plasma polymerization trials were

conducted on a series of model CNC surfaces and the resulting chemistry and morphology of

the MAPP/ CNC nanocomposites were characterized before and after aging. This presentation

will discuss how the pattern of cellulosic model surfaces impact the morphology and chemistry of

the resulting films, thereby shedding light on the nanostructuring role and mechanism of CNCs in

MAPP. 3,4

REFERENCES

1. P. Samyn, A. Airoud, A. Matthew, V. Roucoules and M.-P. Laborie 2012. Metastable Patterning of

Plasma nanocomposite films by incorporating cellulose nanowhiskers, Langmuir, 28, 1427-1438.

2. M. M. Brioude, M.-P. Laborie, A. Airoudj, H. Haidara, V. Roucoules, 2015, Understanding the Morphogenesis of Nanostructures in Maleic Anhydride Plasma Polymer Films via Growth kinetics and Chemical Force titration, Plasma Polymers and Processes 04 (2015), DOI:10.1002/ppap.201400224

3. M. Brioude, A. Airoudj, H. Haidara, M.-P. Laborie and V. Roucoules 2014, Controlling the morphogenesis of needle-like and multibranched structures in maleic anhydride plasma polymer thin films, Plasma Processes and Polymers 11 (10) 943-951

4. M. M. Brioude, V. Roucoules, H. Haidara, L. Vonna, M.-P. Laborie 2015, Role of cellulose nanocrystals on the microstructure of maleic anhydride plasma polymer thin films, Journal of Applied Materials and Interfaces, in Press, DOI: 10.1021/acsami.5b03302

Acknowledgements

M.B. acknowledges the doctoral scholarship from the Elisabeth and Barbara and Grammel Foundation at the University of Freiburg. Short term scientific missions (STSMs) of M. B. to the University of Haute Alsace were supported by the COST Actions FP1006 – “Bringing new functions to wood through surface modification” and FP1205 – “Innovative applications of regenerated wood cellulose fibres”.

Session V:

DESIGNING AND EVOLUTION OF CELLULOSE-BASED NANOFILLERS-DOPED CHITOSAN FILMS

LINDA VECBISKENA, LAURA VIKELE, LINDA ROZENBERGA

LATVIAN STATE INSTITUTE OF WOOD CHEMISTRY, 27 Dzerbenes St., LV 1006, RIGA, LATVIA

ABSTRACT Nowadays, there is a particular interest on natural nanofillers for use as reinforcement into

biopolymer composites (Lee et al. 2014). Along this direction, the cellulose-based nanoparticles

are remarkably versatile materials on which to base a new industry of biopolymer composites

(Moon et al. 2011). Chitosan, the only cationic polysaccharide of natural origin, has been

extensively explored; and its features highlights the suitability and extensive applications that it

has in food, textile and paper industry (Reis et al. 2011), as well as in biomedicine and

pharmacology (Dash et al. 2011). This research takes on the challenge, with attention to

biological properties, to develop the biocomposites, cellulose-based nanofillers-doped chitosan

films, that can be used in packaging industry or biomedicine.

Cellulose-based nanofillers were obtained using the classical methods, acid hydrolysis,

thermocatalytic destruction, TEMPO catalysed oxidation, and a new alternative way, peroxide

group oxidation, that has been developed at Latvian State Institute of Wood Chemistry. These

nanofillers (1–2 wt%) were dispersed in 2% chitosan-acetic acid solution (chitosan: low

molecular weight with a degree of deacetylation 79%) by ultra-sonication (Ultrasonic

Homogenizer Ultrasonic Cell Crusher Sonic 650W, MRC Scientific Instruments, UK). The

biopolymer solution was used to produce the film by film-casting method. Mechanical properties

were evaluated using equipment for testing tensile strength (Frank Tensile Tester, Germany,

DIN EN ISO 1924-1 standard). Films were assessed against Staphylococcus aureus (S. aureus,

gram-positive) and Escherichia coli (E. coli, gram-negative). The cell viability (osteosarcoma cell

line Saos-2) was tested in vitro with an AlamarBlue® cell viability assay (Life Technologies, Italy).

The results showed that chitosan matrix can be successfully tuned by including cellulose-based

nanofillers to improve the physical-mechanical and biological properties. Designed biocomposite

films were non-toxic, as well as showed the ability to promote cell attachment and spreading.

REFERENCES

Dash, M., Chiellini, F., Ottenbrite, R.M., Chiellini, E., (2011). Chitosan – a versatile semi-synthetic polymer in biomedical applications. Prog. Polym. Sci., 36, 981–1014. Lee, K.Y., Aitomaki, Y., Berglund, L.A., Oksman, K., Bismarck, A. (2014). On the use of nanocellulose as reinforcement in polymer matrix composites. Compos. Sci. Technol. 105, 15–27. Moon, R.J., Martini, A., Nairn, J., Simonsen, J., Youngblood J. (2011). Cellulose nanomaterials review: structure, properties and nanocomposites. Chem. Soc. Rev. 40, 3941–3994.

Reis, A.B., Yoshida, C.M.P., Reis, A.P.C., Franco, T.T. (2011). Application of chitosan emulsion as a coating on Kraft paper. Polym. Int., 60, 963–969.

ACKNOWLEDGMENTS Financial support for this research from National Research Program of Latvia is greatly

appreciated. The authors are grateful to Rita Treimane, Laboratory of Industrial Microbiology and

Food Biotechnology, Institute of Microbiology and Biotechnology, University of Latvia, for

microbial culture work. Linda Vecbiskena would like to express her appreciation to COST Action

FP1205 Grant Holder for financial support to realize a Short-Term Scientific Mission at the

Department of Chemistry, Materials and Chemical Engineering “G.Natta”, Milan, Italy.

Session V:

Dispersion and Functionality of Cellulose Nanocrytals

WENWEN FANGa, EERO KONTTURI

b, TIMO LAAKSONEN

c, MARKUS LINDER

d, PÄIVI LAAKSONEN

a

a DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING, SCHOOL OF CHEMICAL TECHNOLOGY, AALTO UNIVERSITY, FINLAND b DEPARTMENT OF FOREST PRODUCTS TECHNOLOGY, SCHOOL OF CHEMICAL TECHNOLOGY, AALTO UNIVERSITY, FINLAND c DIVISION OF PHARMACEUTICAL TECHNOLOGY, FACULTY OF PHARMACY, HELSINKI UNIVERSITY, FINLAND d DEPARTMENT OF BIOTECHNOLOGY AND CHEMICAL TECHNOLOGY, SCHOOL OF CHEMICAL TECHNOLOGY, AALTO UNIVERSITY, FINLAND

ABSTRACT Cellulose nanocrystals (CNC) are of interest as a very attractive material because of the relative

low density (∼1.6 g/cm3), low cost, non-toxic character, high surface area and high modulus of

elasticity (∼130 GPa) (Habibi et al. 2010). They can be isolated from various cellulose sources,

such as wood pulp, cotton, ramie, bacterial cellulose, algae and tunicates by acid hydrolysis

(Klemm et al. 2011). In this work, the CNCs were obtained by hydrolysis of cotton filter paper in a

desiccator saturated with HCl vapor, which provides a simple and fast method for the production

of CNCs. However, the resulting CNCs were still tightly packed in the filter paper and their

colloidal stability was also very low. Therefore, mechanical disintegration of CNCs and

improvement of their colloidal stability by non-covalent modification by additive molecules, such

as cellulose binding proteins and carbohydrates were investigated in this work. Dynamic light

scattering (DLS), high performance anion exchange chromatography (HPAEC), AFM and TEM

were used to characterize the dispersion of CNCs. The dispersed and functionalized CNCs can

further be used in high value-added application and as building blocks for nanocomposites.

REFERENCES

Habibi, Y., Lucia, L.A. and Rojas, O.J. (2010). Cellulose Nanocrystals: Chemistry, Self-

Assembly, and Applications. Chem. Rev. 2010, 110(6), 3479−3500.

Klemm, D., Kramer, F., Moritz, S., Lindström, T., Ankerfors, M., Gray, D. and Dorris, A. (2011).

Nanocelluloses: A new family of nature-based materials. Angewandte Chemie - International

Edition. 50(24), 5438–5466.

Session V:

Study of kinetics of TEMPO-mediated oxidation of nanocellulose by ESR

Juan M. Buffa1, María Alejandra Grela

2, Mirta I. Aranguren

1, Verónica L. Mucci

1

1 Institute of Research in Materials Science and Technology (INTEMA), National University of Mar del

Plata - National Research Council (CONICET), Av. Juan B. Justo 4302, (7600) Mar del Plata, ARGENTINA 2 Department of Chemistry, National University of Mar del Plata-CONICET

ABSTRACT

TEMPO-mediated oxidation of cellulose nanocrystals (CNC) has been widely used as a

selective oxidation of the C6 carbon to obtain carboxyl groups. By this method, high degrees of

oxidation (DO) can be obtained with only a catalytic amount of TEMPO and other inexpensive

reagents, such as NaClO, NaBr and NaOH. The dependence of the DO with the amount of

NaClO has been already reported (Habibi, Chanzy, & Vignon, 2006) as well as some theoretical

approaches on the kinetic of the reaction (Bailey, Bobbitt, & Wiberg, 2007; De Nooy, Besemer, &

Van Bekkum, 1995), but with no quantitative experimental information.

In this work, we measured the evolution of TEMPO concentration through the reaction by

the use of electron spin resonance (ESR) spectroscopy. The correlation between this

concentration, NaClO concentration (determined by iodometry) and DO (by conductimetric

titration) is presented. By the use of reported procedure with optimized amounts of NaClO, we

were able to obtain CNC with a DO of 26%. Additionally, we introduced a new methodology for

the measurement and study of the kinetics of the reaction. Using a pH 10 buffer, we were able to

eliminate the need for adding NaOH aliquots, maintaining the pH approximately constant, and

making possible to determine the TEMPO concentration continuously. All three determined

quantities (TEMPO and NaClO concentration and DO) were fitted using exponential functions

that used the same phenomenological constant.

References

Bailey, W. F., Bobbitt, J. M., & Wiberg, K. B. (2007). Mechanism of the oxidation of alcohols by oxoammonium cations. Journal of Organic Chemistry, 72(12), 4504–4509. http://doi.org/10.1021/jo0704614 De Nooy, a. E. J., Besemer, a. C., & Van Bekkum, H. (1995). Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism. Tetrahedron, 51(29), 8023–8032. http://doi.org/10.1016/0040-4020(95)00417-7 Habibi, Y., Chanzy, H., & Vignon, M. R. (2006). TEMPO-mediated surface oxidation of cellulose whiskers. Cellulose, 13(6), 679–687. http://doi.org/10.1007/s10570-006-9075-y

Presentations STSM:

LIGNIN MODIFICATION BY CARBENE CHEMISTRY

FLORIAN ZIKELIa, HEIKO LANGE

b, CLAUDIA CRESTINI

b

aVienna University of Technology, Institute of Chemical Engineering

. Getreidemarkt 9/166, A-1060 Vienna,

Austria

bUniversity of Rome ‘Tor Vergata’, Department of Chemical Sciences and Technologies

, Via della Ricerca

Scientifica, 00133 Rome, Italy

ABSTRACT Increased production of cellulosic ethanol from lignocellulosic agricultural waste material leads to

big amounts of side-stream straw and grass lignin. Agricultural wastes can be pre-treated for

lignin removal under less harsh conditions than wood and thus conservation of naturally

occurring lignin substructures – e.g., C=C double bonds bearing p-hydroxycinnamic acid

structures – interesting for further usage by organic chemistry methods is possible. Similarly,

lignin modification reactions selective for lignin substructures deriving from pulping reactions –

e.g., C=C double bonds bearing stilbene structures – can create new approaches in lignin

utilization.

Lignin modification experiments were conducted based on a protocol from Ziyat et al. (2006)

modified respective the substrate using industrial wheat straw and Kraft lignin. Chloroform was

used in different molar equivalents with respect to lignin C=C double bonds together with NaOH

for the in situ production of the dichlorocarbene species and tetrabutylmethylammonium chloride

(TBMAC) as a phase transfer catalyst. Modified lignin samples were subjected to GPC analysis

in THF after acetobromination, as well as quantitative 31P-NMR and 2D HSQC NMR

spectroscopy after respective derivatization.

Molar mass distribution effects were noted in the modified lignins. Detection of new cross-peaks

in the 2D NMR spectra area specific for C=C bonds could be observed with WSL. Further, lignin

substructures of stilbene-like type were found increased in the modified lignin both of WSL and

KL. Decreased amounts of the respective free phenolic OH groups in the modified lignins imply

carbene reactions with aromatic rings of G- and H-type through a Reimer-Tillmann mechanism.

REFERENCES

Ziyat, H., Itto, M.Y.A., Ali, M.A., Riahi, A., Karim, A., Daranc, J.C. (2006). Convenient synthesis of new functionalized cyclopropanes from monoterpenic olefins. Arkivoc, 12, 152-160.

Presentations STSM:

WOOD STRUCTURE - MOISTURE CONTENT RELATIONS IN UNMODIFIED AND CHEMICALLY MODIFIED WOOD

CARMEN-MIHAELA POPESCU

a

“PETRU PONI” INSTITUTE OF MACROMOLECULAR CHEMISTRY OF THE ROMANIAN ACADEMY, IASI, ROMANIA

ABSTRACT Wooden cell wall is a complex architecture – the relation between structure and properties and

also moisture content is different between species and also when wood is modified by chemical

treatments and is not fully understand. The aims of the STSM performed at The Norwegian

Forest and Landscape Institute, Ås, Norway was to apply different spectral techniques in order

to better understand the correlation between the water content and the structure of wood – the

affinity of the water molecules with the wood cell wall structure. The interactions that appear

between water molecules and wood structure and the mechanism of adsorption of water by

infrared spectroscopy will be evaluated. For this both NIR and IR techniques were applied.

Presentations STSM:

NOVEL POROUS MATERIALS FROM LIGNIN METHACRYLATES COPOLYMERIZED WITH St AND DVB

O. SEVASTYANOVA

a, O. GORDOBIL

b, B. PODKOŚCIELNA

c, J. LABIDI

b, B. GAWDZIK

c.

a KTH, ROYAL INSTITUTE OF TECHNOLOGY, DEPARTMENT OF FIBRE AND POLYMER

TECHNOLOGY, WALLENBERG WOOD SCIENCE CENTER, STOCKHOLM, SWEDEN. b UNIVERSITY OF THE BASQUE COUNTRY, CHEMICAL AND ENVIRONMENTAL ENGINEERING

DEPARTMENT, SAN SEBASTIAN, SPAIN.

c MARIA CURIE-SKŁODOWSKA UNIVERSITY,DEPARTMENT OF POLYMER CHEMISTRY, LUBLIN,

POLAND.

ABSTRACT The conversion of lignin, one of the three main biopolymers together with cellulose and

hemicellulose in the biomass, to value-added products is an essential part of the integrated

biorefinery concept. Technical lignins are generated as by-products in pulp and paper

manufacturing and in biomass pre-treatment processes, such as in kraft, soda, sulfite,

organosolv, and hydrolysis methods. The structure and properties of such lignin molecules vary

depending on the wood species from which they are derived and, to an even greater extent, on

the industrial process employed to isolate them.

Lignin possesses structural features that make it a promising starting material for chemical

modifications, which can lead to the preparation of valuable polymeric materials. Lignins have

phenolic hydroxyl groups and aliphatic hydroxyl groups at the C-α and C-γ positions on the side

chain, which can be used for chemical modifications to increase the range of lignin applications.

The proportion between the number of phenolic and aliphatic OH-groups in the lignin

macromolecule varies depending on the isolation process (kraft, alkali, organosolv, etc.).

Phenolic hydroxyl are the most reactive functional groups and can significantly affect the

chemical reactivity of the lignin material. By means of the esterification of lignin the new reactive

groups can be introduced into its macromolecular structure to enable it to crosslink with various

polymeric systems. One such example is lignin derivatives with acrylate functionality.

In present work organosolv and kraft lignin isolated from spruce and eucalyptus wood were

modified with methacryloyl chloride as shown in Figure 1a (Naveau, 1975). The successful

introduction of methacrylic groups into lignin structure was confirmed by ATR-FTIR method.

FTIR spectra of modified lignin samples show strong bands at 1175 cm-1 and 1720 cm-1 (C=O

stretch in ester groups), whereas the intensity of broad O-H stretching band (3600-3050 cm-1) is

significantly reduced (see FTIR spectra for eucalyptus lignin at Fig.2).

a)

Lignin + CH3

O

ClL-O

O CH3

b)

+ L-O

O CH3

CH2

CH2

+

CH2

St DVB

or

St-DVB-L orgSt-DVB-L kraft

OH

OCH3

SH

OH

OCH3

OC2H5

Figure 1. Schematic representation of the: a) reaction of lignin with methacryloyl chloride ; b)

copolymerization of kraft and eucalyptus lignin methacrylate derivative with St and DVB.

4000 3500 3000 2500 2000 1500 1000

T (

%)

Wavenumber (cm-1)

OE

OE-MC

4000 3500 3000 2500 2000 1500 1000

T (

%)

Wavenumber (cm-1)

KE

KE-MC

a) Organosolv Eucalyptus lignin: original (OE)

and modified with methacryloyl chloride (OE-MC)

b) Kraft Eucalyptus lignin original (KE) and

modified with methacryloyl chloride (KE-MC)

Figure 2. ATR-FTIR spectra of a) organosolv eucalyptus lignin (OE) and its methacrylic

derivative (OE-MC); b) kraft eucalyptus lignin (KE) and its methacrylic derivative (KE-MC).

Obtained methacrylic derivatives of lignin were co-polymerized with styrene (St) and

divinylbenzene (DVB) to obtain porous functionalized microspheres (Podkościelna et al. 2015).

The schematic representation of synthesis is shown in Figure 1b. Due to the presence of

different functional groups in the lignin macromolecule, lignin-containing porous St-DVB

microspheres are expected to have a potential as sorbents for the removal of chlorinated

phenolic compounds from waste water.

REFERENCES Naveau, H.P. (1975) Methacrylic derivatives of lignin. Cell. Chem. Technol. 9:71-77. Podkościelna, B., Sobiesiak, M., Zhao, Y., Gawdzik, B., O. Sevastyanova (2015), Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene, Holzforschung, DOI: 10.1515/hf-2014-0265

Participants:

1 Abushammala Hatem University of Freiburg Germany

2 Bakirci Ezgi Sabanci University Turkey

3 Bellanger Hervé ETH & Empa Switzerland

4 Berg John ETH & Empa Switzerland

5 Berglund Lars KTH Royal Institute of

Technology

Sweden

6 Borghei Maryam Aalto University Finland

7 Buffa Juan M. National University of Mar

del Plata

Argentina

8 Buffiere Jean Aalto University Finland

9 Bulone Vincent KTH Royal Institute of

Technology

Sweden

10 Burgert Ingo ETH & Empa Switzerland

11 Cabane Etienne ETH & Empa Switzerland

12 Casdorff Kirstin ETH & Empa Switzerland

13 Cunha Gisela Aalto University Finland

14 Czene Tibor SCH-Ózon Kft. Hungary

15 Desseaux Solenne Empa Switzerland

16 Dos Santos Tiago University of Freiburg Germany

17 Dumanli Ahu Gümrah Adolphe Merkle Institute Switzerland

18 Exner Wolfgang WICOR HOLDING AG Switzerland

19 Fang Wenwen Aalto University Finland

20 Friesewinkel Till Empa Switzerland

21 Geiger Thomas Empa Switzerland

22 Gleuwitz Robert University of Freiburg Germany

23 Grosse Charlotte Berner Fachhochschule Switzerland

24 Grüneberger Franziska Empa Switzerland

25 Guo Huizhang ETH & Empa Switzerland

26 Guo Jiaqi Aalto University Finland

27 Gountsidou Vasiliki Aristotle University of

Thessaloniki

Greece

28 Hausmann Michael Empa Switzerland

29 Hua Jin Aalto University Finland

30 Ikkala Olli Aalto University Finland

31 Janiszewska Dominika Wood Technology Institute Poland

32 Josset Sebastien Empa Switzerland

33 Kallio Pasi Tampere University Finland

34 Keplinger Tobias ETH & Empa Switzerland

35 Khakalo Alexy Aalto University Finland

36 Khoushabi Azadeh EPFL Switzerland

37 Kohler Matthias ETH Switzerland

38 Kowaluk Grzegorz Warsaw University of Life

Sciences

Poland

39 Laborie Marie-Pierre University of Freiburg Germany

40 Larsson Tomas Innventia AB Sweden

41 Lozhechnikova Alina Aalto University Finland

42 Mao Jia University of Freiburg Germany

43 Merk Vivian ETH & Empa Switzerland

44 Mikczinski Manuel OFFIS Institute for

Information Technology

Germany

45 Orsolini Paola Empa Switzerland

46 Oven Primoz University of Ljubljana Slovenia

47 Papadopoulo Electra Chimar Hellas S.A. Greece

48 Poljansek Ida University of Ljubljana Slovenia

49 Popescu Carmen Mihaela Romanian Academy IASI Romania

50 Preis Itan Hebrew University of

Jerusalem

Israel

51 Rivkin Amit Hebrew University of

Jerusalem

Israel

52 Robles Eduardo University of the Basque

Country UPV/EHU

Spain

53 Rojas Orlando Aalto University Finland

54 Sedighi-Gilani Marjan Empa Switzerland

55 Sehaqui Houssine Empa Switzerland

56 Siqueira Gilberto Empa Switzerland

57 Segmehl Jana ETH & Empa Switzerland

58 Sevastyanova Olena KTH Royal Institute of

Technology

Sweden

59 Sorieul Mathias University of Cambridge United Kingdom

60 Tadokoro Sandra Empa Switzerland

61 Tarmian Asghar ETH Switzerland/Iran

62 Teheri Hesam University of Freiburg Germany

63 Tingaut Philippe Empa Switzerland

64 Trifol Jon DTU Kemiteknik Denmark

65 Truninger Stefan Weidmann Electrical

Technology AG

Switzerland

66 Turner Philip Edinburgh Napier

University

United Kingdom

67 Vecbiskena Linda Latvian State Institute of

Wood Chemistry

Latvia

68 Wang Ling Aalto University Finland

69 Weishaupt Ramon Empa Switzerland

70 Wilson Benjamin Aalto University Finland

71 Wolfinger Tobias Weidmann Electrical

Technology AG

Switzerland

72 Xiang Wenchao Aalto University Finland

73 Zikeli Florian Vienna University of

Technology

Austria

74 Zimmermann Tanja Empa Switzerland

Documents

COST Action FP1105 workshop: Functional wood and …/media/documents/sebe/cost-action/events/... · COST Action FP1105 workshop: Functional wood and cellulose-based materials 31.08