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Cellulosic Materials – Processing,
Properties and Promising
Applications
Joint Working Groups &
Management Committee Meetings
September 22-23, 2016
Budapest
COST ACTION FP1205 BUDAPEST 22-23 September 2016
Cellulosic Materials – Processing,
Properties and Promising Applications
Joint Working Groups & Management
Committee Meetings
September 22-23, 2016
Venue
Rubin Wellness & Conference Hotel, Akvamarin Room
Dayka Gábor u. 3. H-1118 Budapest
Budapest University of Technology and Economics
Budapest University of Technology and Economics
Faculty of Chemical Technology and Biotechnology
Department of Physical Chemistry and Materials Science
Budapest, Hungary
COST ACTION FP1205 BUDAPEST 22-23 September 2016
WELCOME
Most welcome everyone to Budapest to join us in the upcoming joint working groups
and management committee meeting within the Cost Action FP1205 “Innovative
Applications of Regenerated Wood Cellulose Fibres” chaired by Dr. Åsa Östlund.
The working groups meeting will run from the morning of Thursday the 22nd of
September until lunch time on Friday the 23rd of September 2016. Subsequently, the
6th Management Committee meeting starts after lunch on Friday.
The aim of the workshop is to provide support on new product area development around
the theme “Cellulosic materials - processing, properties and promising applications”
related to COST FP1205 and to spread the knowledge to the wider scientific
community on the current and upcoming commercial processes as well as some of
the most promising methods identified in the first 3 years of the Action. The workshop
will comprise of selected keynote speakers to show their recent developments, and
how these have been linked to the COST Action. The agenda will cover key activities
from each Working Group in the Action as well as develop follow up on ideas for the
end of the Action. These ideas will then be presented at the Management Committee
for consideration and adoption during the final period of the Action.
Budapest Unversity of Technology and Economics
The university and the Department of Physical Chemistry and Materials Science will
be introduced shortly at the beginning of the conference on Thursday.
Budapest
Budapest is undoubtedly one of the most beautifully located cities in the world. Buda is
built on a hill on the west bank of the river Danube and forms the historical part of the
city. Pest stands on a plain and it is more businesslike with its shops and boulevards.
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AGENDA
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST FP1205 Meeting
Budapest, Hungary
September 22-23, 2016
Workshop on:
Cellulosic materials - processing, properties and promising applications
Budapest University of Technology and Economics (BME)
Faculty of Chemical Technology and Biotechnology
Department of Physical Chemistry and Materials Science
AGENDA
Day 1. Thursday - September 22, 2016
08:30
Registration
09:00
Åsa Östlund (SP, SE) and Emília Csiszár (BME, HU)
Krisztina László – Vice-Rector for International Affairs
Budapest University of Technology and Economics
Alfréd Menyhárd - Head of Laboratory
Laboratory of Plastics and Rubber Technology
Department of Physical Chemistry and Materials Science
Welcome
Session 1 - KEYNOTE LECTURE 1
9:20
Thomas Rosenau (BOKU, AT):
Towards a better understanding of cellulose swelling, dissolution, regeneration and phase
transition (cellulose I  II) on the molecular level
10:20
Coffee
SESSION 1: ORAL PRESENTATIONS
10:40
Ulf Germgård (Karlstad University, SE):
Integration of a sulfite pulp mill and a viscose plant
11:00
Nandual Wanasekara (University of Exeter, UK):
Molecular deformation and orientation in ionic liquid spun cellulose fibers
11:20
Paola Orsolini (EMPA, CH):
Dense and porous nanofibrillated cellulose substrates
POSTER PRESENTATIONS I
11:40
P1 – Tal Ben Shalom (The Hebrew University of Jerusalem, IL): Novel environmental
friendly new method for crosslinking of cellulose nanocrystals (CNCs) via esterification
P2 – Arthur Werner (Univ. Bordeaux, FR): A novel method to produce polymer
nanolatexes by Pickering emulsification with cellulose nanocrystals (CNCs)
P3 – Vanja Kokol (Univ. Maribor, SI): In situ synthesised NanoCellulose – Hydroxyapatite
based composites for phenol and cobalt adsorption
COST ACTION FP1205 BUDAPEST 22-23 September 2016
P4 – Mariusz Mamiński (Warsaw University of Life Sciences, Pl): Cellulose degradation
products as a raw material for PUR foams
P5 – Levente Csóka (University of West Hungary, HU): Surface chemistry of
sonochemically-treated bacterial cellulose
P6 – Chiara Bongio (Politecnico di Milano, IT): Bacterial nanocellulose
glycidylmethacrylate grafting. Preparation and perspective
P7 – Kay Hettrich (Fraunhofer Institute for Applied Polymer Research, DE): Preparing of
nanoparticles from partly derivatized cellulose
P8 – Renata Toczyłowska-Mamińska (Warsaw University of Life Sciences, Pl):
Perspective use of solubilised cellulose in microbial fuel cells (MFCs)
P9 – Zvi Shtein (The Hebrew University of Jerusalem, IL): Spider silk-CBD-CNC
composites: mechanism of assembly
P10 – Sebestyén Nagy (Budapest University of Technology and Economics, HU):
Production and properties of nanocrystalline cellulose suspensions and films
12:00
Lunch and Posters
SESSION 2: KEYNOTE LECTURE 2
13:45
Stephen Eichhorn (University of Exeter, UK):
Electrospun nano-fibres for bio inspired composite materials and innovative industrial
applications
SESSION 2: ORAL PRESENTATION
14:45
Jose M. Lagaron (Novel Materials and Nanotechnology Group, IATA-CSIC, ES):
Nanocellulose to taylor the barrier performance of electrospun biopolyester coatings and
layers for food packaging applications
15:25
Coffee and Posters
SESSION 2: ORAL PRESENTATIONS
16:00
Eduardo Robles (University of the Basque Country UPV/EHU, ES):
Heterogeneous silanization of cellulose nanofibers with 3-aminopropyl triethoxysilane
16:20
Victor Kisonen (Bi-Co, FI):
Cellulose in horticultural applications
16:40
End of Day 1
17:00
Walk in the city - optional
(From Szt. Gellért square either up to the Citadella or to the campus of BME)
19:30
Conference Dinner
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2
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
Day 2. Friday – September 23, 2016
Session 3 - KEYNOTE LECTURE 3
9:00
Kristiina Oksman (Luleå University of Technology, SE)
Cellulose nanofibers from industrial residues and their use in composite materials
SESSION 3: ORAL PRESENTATIONS
10:00
Marc Delgado-Aguilar(University of Girona, ES):
Hydrophobic nanocellulose-based aerogels for selective oil removal: an effective and
simple method
POSTER PRESENTATIONS II
10:20
P11 – Benjamin Dhuiège (University of Bordeaux, LCPO, FR):
Synthesis and characterisation of nanocellulose aerogels for the elaboration of innovative
and biosourced bone substitutes
P12 – Linda Vecbiskena (Latvian State Institute of Wood Chemistry, LV)
100% recycled paper packaging materials: processing, properties and potential
application
P13 – Alena Šišková (Polymer Institute of Slovak Academy of Sciences, SK): Cellulosebased controlled-release agrochemicals formulation
P14 – Alican Gençe (KU Leuven, BE): Influence of the particle concentration and
Marangoni flow on the formation of cellulose nanocrystal films
P15 – Tufan Salan (Kahramanmaras Sutcu Imam University, TR): Bio-based foams from
renewable and sustainable polyols obtained by liquefaction of lignocellulosics
P16 – Bianca-Ioana Dogaru (Petru Poni Institute of Macromolecular Chemistry, RO):
Analytical methods for the investigation of the water - biodegradable films interaction
P17 – Imola Herceg (Budapest University of Technology and Economics, HU):
Interaction of water with CNC films
P18 – David Leibler (Hebrew University of Jerusalem, IL): Nanocomposite films based on
cellulose nanocrystals and titanium dioxide nanoparticles
P19 – Amit Rivkin (Hebrew University of Jerusalem, IL): Bio-inspired nanocomposite films
and foams from resilin-CBD bound to cellulose nanocrystals
10:40
Coffee and Posters
SESSION 3: ORAL PRESENTATIONS
11:00
Helena Oliver-Ortega (Universitat de Girona, ES):
Preliminary results of the application of carboxymethylated cellulose as a reinforcing
agent in papermaking
11:20
Noemi Merayo (Complutense University of Madrid, ES):
Relevance of retention systems when using cellulose nanofibers as strength additives in
papermaking
12:00
End of Workshop
Lunch
MANAGEMENT COMMITTEE MEETING
Participants: MC members and MC substitutes (all visitors are welcome but only MC members’ votes
counts in decision making)
13:30
Åsa Östlund (SP, SE)
15:30
End of meeting
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ABSTRACTS
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
1 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
1 22-23 September 2016
Towards a better understanding of cellulose swelling, dissolution,
regeneration and phase transition (cellulose I  II)
on the molecular level
mercerization with concentrated lye. It is commonly accepted that in cellulose the
chains are in parallel arrangement, while cellulose II has an antiparallel chain
orientation. The transition from parallel cellulose I to antiparallel cellulose II can be
easily understood if the 'detour' via completely dissolved cellulose is involved: the
cellulose chains are separated in solution and will re-aggregate as the
thermodynamically most stable allomorph, which is cellulose II. However, how the
parallel-to-antiparallel transition in solid state (during mercerization) can be imagined is
still a mystery and one of the oldest riddles in cellulose science. We will add some
pieces to the jigsaw puzzle of the solid-state cellulose I to cellulose II transition
(evidently without being able to arrange those pieces into a final, nicely ordered
picture), in particular addressing the axiom that always cellulose II is regenerated from
cellulose solutions. It will be demonstrated that special regeneration conditions that
align the reducing ends to one side through temporary derivative formation allow
reprecipitating cellulose I from solution, independent of whether a cellulose I substrate
(such as a cellulosic pulp or cotton linters) or a cellulose II substrate (such as viscose
fibers) had been dissolved. The latter case represents something like a 'reverse
mercerization' with regard to the allomorph change. The experiments involve different
cellulosic substrates, and the transitions are studied by means of solution and solid-state
NMR, light scattering as well as X-ray diffraction experiments.
Thomas Rosenau,1 Antje Potthast,1 Markus Bacher,1 Fumiaki
Nakatsubo,2 Alfred D. French,3 Bob Blant,4 Kanji Kajiwara,5 Kurt
Mereiter6
1
BOKU University Vienna, Austria, Department of Chemistry, Division of Chemistry of
2
Renewable Resources; Lab of Active Bio-based Materials, Kyoto University, Japan; Kyoto
3
University, Japan, Uji Research Center; Southern Regional Research Center, U.S.
4
5
Department of Agriculture, Metairie, Louisiana, USA; Shinshu University, Japan; Harvard
6
Nanorobotics Center, USA; Vienna University of Technology, Austria
Keywords: cellulose, dissolution, H-bond system, phase transition, swelling,
regeneration
ABSTRACT
The exact structure of the hydrogen bond networks and the changes of these networks
upon swelling and dissolution processes are current ‘hot topics’ in cellulose research. Hbonds are responsible for the allomorphism of cellulose, for the typical properties of
cellulose, and for reactivity and chemical behavior. The use of isotopic labeling with
modern solid-state NMR techniques in combination with X-ray crystal structure
analysis is a powerful approach to obtain solid state and gel structural data of cellulose
and cellulose model compounds, so that we now come closer to an understanding of
cellulose swelling and dissolution on a molecular level, and might even successfully
address the old and unanswered question about the special nature of cellulose solvents.
With the 13C-perlabeled solutes (cellulose model compounds and celluloses), novel
solid-state NMR experiments that were based on the high degree of isotopic enrichment
(>99%) became possible. Protons in hydrogen bonds (C-O-H…O-C motifs) are detected
through the two carbons that are bridged by this proton. The cleavage and re-formation
of the complex hydrogen bond network became accessible to detailed analysis for the
first time. We selected the following cellulose solvents for our studies, which were
synthesized in perdeuterated and 15N-labeled form: NMMO, DMAc, and BMIM acetate.
15
N-labeling in addition to perdeuteration allows measuring the defined distance
between solvent nitrogen and the respective cellulose (model) carbon, and thus
monitoring approach and action of the solvent.
The studies showed that swelling is a reversible process of 3-4 stages, connected with
cleavage of hydrogen bonds mainly to/from OH-6 and OH-2. Dissolution, by contrast,
is irreversible and involves in addition H-bonds to/from OH-3. In addition to common
O-H hydrogen bonds, cellulose solvents also form non-conventional C-H hydrogen
bonds, involving exclusively CH-1 and CH-3, but no other carbon positions, which
might be a prerequisite to cellulose dissolution. All these molecular level data are
available for the first time and provide a consistent picture of the molecular mechanisms
of swelling and dissolution of cellulose and cellulosic model compounds, which will be
presented in this lecture.
The allomorphism of cellulose is a wellknown fact. Cellulose I and cellulose II are the
most important allomorphs, the former term describing 'native' cellulose, the latter being
cellulose that has either been regenerated from cellulose solutions or obtained by
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
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BUDAPEST
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COST ACTION FP1205 SESSION
BUDAPEST
1 22-23 September 2016
RESULTS AND DISCUSSION
Integration of a sulfite pulp mill and a viscose plant
Hans Magnusson, Gunnar Henriksson, Ulf Germgård
The four pulping alternatives for sulfite dissolving pulp production integrated with a
traditional viscose plant are shown in a simplified manner in Fig.1.
Karlstad University, Department of Engineering and Chemical Sciences, SE 65188 Karlstad,
Sweden, [email protected], [email protected]. [email protected]
Keywords: integration, magnesium, sodium, sulfite pulp, viscose
ABSTRACT
Protection of our global environment has become an important issue for more and more
people and it is today well accepted in all countries that the pollution of our
environment must go down if we are going to survive. One way to reduce the impact on
our environment is to reuse matter and products that earlier were considered as being
waste products. These were thrown away even if they were possible to use much longer.
The same goes for industrial waste streams which often have been sent to the sewer
even though they have contained many useful products which could have been reused
many times. Thus the global population increases and so does the wealth of the people
and especially so for the middle class both in the developed and the developing
countries. This has resulted in a situation that for example China is now consuming
more products and energy than the whole of Europe. More people with more money to
spend means that an increasing number of products are consumed and this is good for
the business life but very bad for the environment.
The increasing purchasing power has considerably raised for example the consumption
of textiles and the increase in the demand is assumed to continue during the next 30-50
years. At the same time is the possibility to considerably increase the production of
cotton non-existing of several reasons and to increase the production of oil based textile
fibers is also problematic as this will lead to increasing carbon dioxide emissions. One
way to solve this dilemma is to base future textile production to a high degree on
sustainable raw materials for example cellulose from trees in the forests. Such cellulose
can be used to produce for example conventional viscose but the viscose process is by
tradition both very polluting leading to both emissions that can catch fire or even
explode and the gas emissions are toxic and thus harmful to the operators of such a
plant. The viscose fibers as such are on the other hand very good. We have therefore
started a project where we try to produce more viscose fibers based on cellulose but we
also try to reuse the current waste steams as much as possible both in the viscose plant
and in the dissolving pulp mill.
The first part of this study discussed the integration of a prehydrolysis kraft pulp mill
and a viscose plant and this has already been published (Magnusson 2016). The current
study can be considered as being the second case of integration of a pulp mill and a
green viscose plant. Thus, we have studied the case where a sulphite pulp mill and a
viscose plant are connected. The pulping process has been either a sodium or a
magnesium sulphite dissolving pulp mill where the pH in the cook has been either 1,5
throughout the cook or initially 4,5 which has been reduced to 1,5 in the second part of
the cook
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Figure 1: A sulfite dissolving pulp mill and an integrated traditional viscose plant . In the pulping
stage either sodium or magnesium is used and the pH in the first stage is either 4,5 /1,5 or just 1,5.
A number of benefits can be achieved if a dissolving pulp mill and a viscose plant are
connected and the most obvious are the following: The energy saving obtained as the
pulp is not fully dried between the pulp mill and the viscose plant. It is naturally easier
to reuse a waste stream if the pulp mill is using sodium as base instead of magnesium. If
sodium is the base a conventional oxygen delignification stage with filtrate recycling
can easily be included in the bleach plant. An oxygen stage based on MgO as alkali is
an option for magnesium based sulphite mills but such a stage performs relatively poor
if the temperature is unchanged. If the temperature is raised 20-30 oC the delignification
will be OK but the selectivity measured as viscosity goes down significantly. Sulfuric
acid is often needed in the bleach plant and in the spinning stage and sulfur rich gases in
the pulp mill could be utilized for such production. The discharge streams contain high
amounts of hemicellulose and lignin and these should naturally be taken care of.
However, also when these components are separated the filtrate streams are interesting
as water is needed for dilution and washing etc. Thus, the combined pulp mill and
viscose plant will have a much lower pollution impact than if these were located
independently from each other.
Carbon disulfide is used in the viscose process but it is a chemical difficult to handle
because of its poisonous properties and the risk for explosions. CS2 can be produced onsite based on carbon and elemental sulfur as raw material.
CONCLUSIONS
Integration of a dissolving pulp mill and a viscose plant has many benefits with respect
to improved process economy and reduced pollution of the environment. For a sulfite
pulp mill the best option is if the cation (the base) is sodium instead of magnesium.
REFERENCES
Magnusson, H., Kvarnlöf N., Henriksson G. and Germgård U. (2016). Integrating
prehydrolysis kraft pulping of softwood and viscose fiber manufacturing. Appita (69) 3,
264-272.
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
1 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
1 22-23 September 2016
Molecular deformation and orientation in ionic liquid spun
cellulose fibers
Functional dense and porous nanofibrillated cellulose substrates
1
2
Paola Orsolini1,2, Carlo Antonini1, Thomas Geiger1, Tanja
Zimmermann, Walter R. Caseri2.
3
Nandula D. Wanasekara , Anne Michud , Chenchen Zhu , Sameer
Rahatekar4, Herbert Sixta5, Stephen J. Eichhorn6
1
2
College of Engineering, Maths and Physical Sciences, Harrison Building, North Park Road,
University of Exeter, UK
Department of Forest Products Technology, Aalto University, P.O. Box 16300, Vuorimiehentie
1, Espoo, FI-00076, Finland
3
Advanced Composites Centre for Innovation and Science (ACCIS), Aerospace Engineering,
University of Bristol, Bristol, UK
1
2
Empa, Swiss Federal Laboratories for Materials Science and Technology, Applied Wood
Materials, Dübendorf, Switzerland. [email protected]
Eidgenössische Technische Hochschule (ETH),Multifunctional Materials, Zürich, Switzerland.
Keywords: methyltrichlorosilane,
superhydrophobicity
nanofibrillated
cellulose,
oil
remediation,
ABSTRACT
Keywords: Ionic Liquid, Cellulose, Molecular Deformation
ABSTRACT
Solubility of cellulose in Ionic liquid offers a sustainable alternative to traditional
processing methods for fibers. The deformation micromechanics and structure-property
relationships are not well understood on ionic liquid spun fibers. In this work, we have
explored the molecular deformation and crystal orientation of cellulose fibers, produced
from an ionic liquid solvent spinning system. The orientation of molecules relative to
the long axis of the fiber was mapped using Raman spectroscopy by monitoring the
change in intensity of a Raman band located at 1095 cm-1. Wide angle X-ray diffraction
was used to understand the crystal orientation of fibers showing higher orientation of
crystals for fibers with higher draw ratios. Tensile testing of these fibers disclosed that a
significant increase of Young's modulus and tensile strength was observed when the
fiber draw ratio is increased from 1 to 6. A crystalline chain slip model was used to
predict the Hermans' orientation parameter values for each draw ratio and a good match
between data and the model suggest dominant crystalline affine deformation along the
longitudinal fiber axis. The findings of this work have lead to recommendations to
improve the elastic moduli of the fibers further. In order to increase the mechanical
properties of fibers, a reduction of chemical and physical impurities in the fibers and an
increase in the total molecular and crystal orientation is essential. Another important
factor in increasing the modulus is to minimize the skin-core differences that exist in the
degree of preferred orientation of crystals (Gindl et al. 2006, Kong et al. 2012). En
enhanced modulus may be achieved by a more uniform orientation of molecules and
crystals in both skin and core of the fiber.
In the last decades, nanofibrillated cellulose (NFC) has gained interest not only as
reinforcing material in polymer composites, but also as building block for dense and
porous substrates. Among the most promising applications in our laboratory, main
efforts have been made to develop membranes and oil-sorbent foams to target
applications such as water purification and oil-pollution remediation. In the present
work, we characterized the porosity of dense membranes by means of different
techniques (Fig. 1), such as mercury intrusion, gas adsorption and thermoporometry
(Orsolini, Michen et al. 2015). Such membranes were produced by a traditional papermaking process from a water-based NFC suspension which led to a highly compact
structure (porosity ~5%), thus their permeance was not competitive with commercial
membranes. Therefore, we focused on enhancing the permeance by a templating
approach based on the use of calcium carbonate nanoparticles. Thanks to this strategy,
the permeance could be increased by one order of magnitude. We further worked on the
chemical functionalization of the NFC substrates with methyltrichlorosilane to grow
polysiloxane nanofibers on their surfaces (Fig. 2). In this case, the amphiphilic
behaviour of cellulose was changed to foster oil-adsorption and water repellence at the
same time. In this part of the study dense membranes, porous membranes and foams
were modified to benefit from the combination of silane chemistry and different surface
roughness to achieve superhydrophobicity and enhanced the oil-adsorption capacity.
REFERENCES
Gindl. W., Martinschitz. K.J., Boesecke, P., Keckes, J. (2006) Orientation of cellulose
crystallites in regenerated cellulose fibres under tensile and bending loads. Cellulose,
13, 621–627.
Kong, K., Deng, L., Kinloch, I. A., Young, R. J., Eichhorn, S. J. (2012) Production of
carbon fibres from a pyrolysed and graphitised liquid crystalline cellulose fibre
precursor. Journal of Material Science, 47, 5402–5410.
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Figure 1: Characterization of cellulose substrates by means of different techniques.
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
1 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
Novel environmental friendly new method for crosslinking of
Cellulose Nanocrystals (CNCs) via esterification
T. Ben Shalom1, A. Rivkin1, T. Abitbol1, Y. Nevo1, S. Lapidot2, O.
Shoseyov1
1
Figure 2: a) NFC foam, b) NFC porous membrane and c) Polysiloxane
nanofilaments grown on a NFC membrane
REFERENCES
Orsolini, P., B. Michen, A. Huch, P. Tingaut, W. R. Caser and T. Zimmermann (2015).
Characterization of Pores in Dense Nanopapers and Nanofibrillated Cellulose Membranes: A
Critical Assessment of Established Methods. Acs Applied Materials & Interfaces, 46, 2588425897.
The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew University of
Jerusalem, Rehovot 76100, Israel
2
Melodea Ltd. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew
Universit y of Jerusalem, Rehovot 76100, Israel. [email protected]
ABSTRACT
Nanocrystalline cellulose (NCC) is grown under controlled conditions that lead to
formation of high-purity single crystals, CNCs from sulfuric acid hydrolysis form stable
suspensions in water due to repulsive interactions from charged groups grafted on
during hydrolysis and exhibit interesting self-assembly, optical and mechanical
properties that make them suited for a wide range of applications. Carboxylic acids were
found to be good cellulose crosslinking agents, whereas the polycarboxylic acid 1,2,3,4butanetetracarboxylic acid (BTCA) was found to be one of the best performing
polycarboxylic acids. Sodium hypophosphite (NaH2PO4) is a most effective catalyst for
catalyzing a reaction with BTCA. This method serves the textile industry for
crosslinking of cotton cellulose to improve anti-pilling, wrinkle recovery, antimicrobial,
water repellent and flame retardant properties of the cotton fabric. In the current work
BTCA and NaH2PO4 (SHP) are used to crosslink CNC. The combination of
crosslinking system with CNC results unexpected new high performing material.
CNC esterification with a polycarboxylic acid begins with the formation of a cyclic
anhydride, followed by covalently binding to a hydroxyl group (-OH group) of the
CNC, forming an ester bond. CNC cross-linked films were prepared by spreading the
aqueous suspensions of CNC/BTCA/SHP onto flat glass followed by water evaporation
under ambient conditions. We were interested in understanding the mechanical
properties of films made by combining one of nature’s strongest materials, CNCs, with
environmental friendly nontoxic crosslinking method, the mechanical tests used to
evaluate the effect of BTCA/SHP cross linking on the material properties of CNC films.
The Instron tests were in tensile mode, whereas the Instron testing shows the results for
CNC/BTCA/SHP, and neat CNC films. Overall, the results highlight that the
mechanical behavior of the films. The cross linked films displayed a significant increase
in the average moduli and tensile stress and strain values at break, resulting in tougher
films on average . The crosslinked CNC films were easier to handle since they were less
brittle. In comparison to the other CNC films studied, CNC/BTCA/SHP films had
higher average moduli and tensile stress and strain values at break 2to 4-fold compared
to neat CNC.
As describe above the crosslinked CNC films exhibited unexpected enhancement in the
mechanical properties in comparison to regular CNC films and also appear to be more
transparent that uncrosslinked films. The alignment of the NCC in the films was
explored using polarized optical microscopy coupled with an image processing module
that is able to confer the direction of sample alignment. The neat CNC films are
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
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COST ACTIONPoster
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22-23 September
2016
presentations
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COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
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birefringent and show the typical fragmented, multi-domain order that is characteristic
of CNC films prepared by water evaporation. In contrast, the CNC cross linked films
appear uniformly birefringent and the polarized microscopy image processing technique
interprets long-range nematic order. To the best of our knowledge, this is the first report
of alignment induced in CNC by BTCA/SHP. Future research should combine
disciplines from different fields of biology, materials engineering and polymers
engineering in order to further improve and adjust the mechanical properties of such
composites according to the required applications in the biomedical fields as well as
other industrial fields such as sports, automotive, construction and more as bio-based
replacement for synthetic materials.
.
A novel method to produce polymer nanolatexes by Pickering
emulsification with modified cellulose nanocrystals (CNCs)
Arthur Werner1, Gilles Sèbe1, Valérie Heroguez1,
University of Bordeaux, ENSCBP, Laboratoire de Chimie des Polymères Organiques,
Bordeaux, France. [email protected]
1
Keywords: Nanolatex, Pickering emulsion, Acetylated CNCs
ABSTRACT
Polymer nanolatexes are nanosized polymer materials with unique properties, which can
find applications in a wide range of domains such as paint, films or rubbers. Their
preparation is usually performed by miniemulsion polymerization, using chemical
surfactants (Hu, Zhang and Yang) or inorganic Pickering stabilizing particles (Bon and
Colver 2007), which are rarely sustainable and can be toxic. These synthetic procedures
are also generally tricky and require harsh reaction conditions.
In this context, we report a new simple strategy to synthesize surfactant-free
nanolatexes, by Pickering emulsification with modified cellulose nanocrystals (CNCs)
(Fig 1). The hydrophilic/hydrophobic balance at the CNCs surface was monitored by
acetylation with vinyl acetate, to produce nanoparticles that can serve as Pickering
surfactant for the stabilization of styrene-in-water emulsions. The controlled
polymerization of the stabilized monomer droplets was subsequently achieved, leading
to the production of nanolatex composed of polystyrene nanobeads in a relatively high
yield. The impact of CNCs concentration, acetylation level and initiator concentration
on the dimensions of the nanobeads produced will be particularly discussed.
Figure 1: a) TEM microscopy of the nanobeads escaping from the Pickering droplets.
b) TEM microscopy of the polystyrene nanolatex.
REFERENCES
X. Hu, J. Zhang, W. Yang, (2009), Preparation of transparent polystyrene nano-latexes
by an UV-induced routine emulsion polymerization. Polymer, 50, 141–147
S. A. F. Bon and P. J. Colver, (2007) Pickering miniemulsion polymerization using
laponite clay as a stabilizer, Langmuir, 23, 8316-8322
20
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
In situ synthesised NanoCellulose – Hydroxyapatite based
composites for phenol and cobalt adsorption
Cellulose degradation products as a raw material for PUR foams
1
1
Vijaykiran N. Narwade , Rajendra Khainar , Vanja Kokol
2
1
School of Physical Sciences, S.R.T.M. University, Nanded, Maharashtra, India.
Sylwia Witek1, Paweł Parzuchowski2 , Mariusz Mamiński1
Warsaw University of Life Sciences – WULS, Faculty of Wood Technology, 159
Nowoursynowska St., 02-787 Warsaw, Poland. [email protected]
1
2
2
University of Maribor, Faculty of Mechanical Engineering, Maribor, Slovenia;
[email protected]
Warsaw University of Technology, Faculty of Chemistry, 3 Noakowskiego St.,
00-664 Warsaw, Poland
Keywords: Composite, Hydoxyapatite, NanoCellulose, Wastewater cleaning
Keywords: agrowaste, cellulose degradation, foam, wood liquefaction
ABSTRACT
The present study deals with the in situ synthesis of Cellulose NanoFibrils (CNFs) and
TEMPO oxidized CNFs with precursors of Hydroxyapatite (HAp) to nanocomposites,
and their relevance for eradicating organic pollutant i.e. phenol and cobalt from the
waste water. The prepared samples are characterized by X-ray diffraction and Fourier
Transform Infrared spectroscopy reveals the formation of HAp. The surface and
morphology characteristics of the native and CNF-HAp composites are verified by
Scanning Electron Microscopy showing well growth occurred HAp platelets on the
nanocellulose matrix and the porous nature of composites. The prepared samples were
used to evaluate phenol and cobalt adsorption kinetics as a function of pH, and the
maximum adsorption capacities were calculated from the kinetic models.
Acknowledgements. The work was supported financially by the Erasmus Mundus
project Euphrates (2013-2540/001-001-EMA2).
ABSTRACT
The environmental policy of the 21st century imposes the maximized utilization of the
cellulosic raw materials. The approach regards agrowaste too. Malaysian and
Indonesian oil palm (Elaeis guineensis) plantations generate huge amounts of waste
trunk. The quantity is estimated on 5 million tonnes annualy. The feedstock is still
unutilized and new pathways of its conversion are welcomed. The content of
holocellulose and α-cellulose in the material is 73% and 33%, respectively.
Thus, the purpose of this study was to investigate the possibility of use liquefied palm
oil wood as polyols for the production of polyurethane foams. Application of palm
wood for PUR production would be an opportunity for use readily available material at
industrial scale.
Liquefaction is an acid-catalyzed chemical degradation of cellulose in presence of
phenol, glycols, glycerol or cyclic carbonates (Yamada and Ono, 1999). The solvolysis
yields a mixture of cellulose and hemicelluloses degradation products that can be used
as polyols for polyurethanes or building blocks for various types of polymers (Kunaver
et al. 2010, Kobayashi et al. 2004) (Fig. 1). Thus, so-called “liquefied wood” can be a
cellulose-derived resource of the components for PUR foams (Pan et al. 2012).
Figure 1: Solvolysis of cellulose
Wood of density 297±30 kg/m3 was ground and sorted. The fraction < 32 mm was used
for further work up.
The liquefaction procedure was as follow: 65 min at 150°C and 65 min at 180°C in a
mixture of ethylene glycol/glycerol (1:1, vol/vol) containing 3%wt of sulfuric acid.
Products of the liquefaction were diluted with dioxane/water (4:1, vol/vol), filtered off
and concentrated. The determined hydroxyl value (LOH) of the polyol was 700 mg
KOH/g. Molecular weight distribution (MALDI-TOF) of the liquefaction products was
below 750 Da (Fig. 2) which proved a complete degradation of cellulosic material.
22
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
Surface chemistry of sonochemically-treated bacterial cellulose
Dimitirios Tsalagkas1, Leena-Sisko Johansson2, Orlando J. Rojas2,
Levente Csoka3
1
Inha University, Department of Mechanical Engineering, 21999 Incheon, South Korea.
[email protected]
2
Figure 2: MALDI-TOF spectrum of the liquefaction products
Aalto University, Department of Forest Products Technology, 16100 Espoo, Finland
[email protected]
3
The liquefied wood products were used as a biopolyol for the preparation of
polyurethane foams. Liquefied wood comprised 0% to 100% of the formulation in a
mixture with polypropylene glycol (PPG). The isocyanate (PMDI) index was adjusted
to 1.05.
The following conclusions were withdrawn from the obtained results:
1. The approach allows to increase utilization of high-cellulose agrowaste in PUR
foams manufacturing.
2. The content of the biopolyol exhibited the influence on the foaming start time
that was shortened from 30 s to 10 s when biolpolyol amount increased from 0%
to 100%. On the other hand, foam tack-free times were lengthened from 100 s to
540 s.
3. The density of foams was affected by the content of degraded cellulose products
in a formulation (16–26 kg/m3 for 30% to 100% of liquefied wood).
4. Stability of the foams was comparable to those of the commercial PUR foams.
Shrinkage of the sample after heating for 72 hrs at 80°C ranged from 1.8% to
6.6% and depended on the degraded cellulose products content (30%–100%).
REFERENCES
Kobayashi M., Asano T., Kajiyama M., Tomita B., (2004). Analysis on residua
formation Turing Wood liquefaction with polyhydric alcohol. Journal of Wood Science,
50, 407-414.
Kunaver, M., Medved, S., Čuk, N., Jasiukaityte, E., Poljanšek, I., Strnad, T., (2010).
Application of liquefied wood as a new particle board adhesive system. Bioresource
Technology, 101, 1361-1368.
Pan, H., Zheng, Z., Hse, C.Y., (2012). Microwave-assisted liquefaction of wood with
polyhydric alcohols and its application in preparation of polyurethane (PU) foams.
European Journal of Wood and Wood Products, 70, 461-470.
Yamada, T., Ono, H. (1999). Rapid liquefaction of lignocellulosic waste by using
ethylene carbonate. Bioresource Technology, 70, 61-67.
24
University of West Hungary, Institute of Wood Based Products and Technologies,
9400 Sopron, Hungary
[email protected]
Keywords: microbial cellulose, XPS, ultrasound
ABSTRACT
Bacterial cellulose (BC) is a material relevant to several applications, including
biomedical, nanocomposite and smart/electric systems. The surface properties of BC
such as surface charge, chemical composition, reactivity and accessibility are strongly
associated to the interfacial interactions of BC fibrils, their modification and
performance. The production of BC as well as the factors which influence BC yield and
its physicochemical properties have been investigated. The aim of this research is to
examine the surface composition of a commercially available, pristine BC (from nata de
coco) before and after sonochemical treatment of alkaline purified BC, through X-ray
photoelectron spectroscopy (XPS).
BC (PT Cocomas, Indonesia) was washed and soaked in pure water several times in
order to remove citric acid and other components in the nata de coco syrup and blended,
after which the material was oven dried at 50℃. A portion of the washed BC was
further purified by alkaline treatment (0.01 M NaOH at 70℃ for 2 h under continuous
stirring) blended and oven dried. Dry samples were redispersed (0.1% w/w), and
ultrasonicated (cold water bath, 30 min, 25 W cm-2) and these BC dispersions were
dried for a second time into nanostructural, self-assembled thin films.
The XPS surface chemical analysis of the BC films was recorded using a Kratos
Analytical AXIS ULTRA electron spectrometer with monochromatic A1 Kα irradiation
at 100 W and under neutralization. Whatman cellulose filter paper, analysed with the
samples, was used as a reference for pure cellulose.
The relative atomic concentration and surface chemical groups determined by XPS are
given in Table 1. Fig. 1 shows the typical wide-scan and high resolution spectra for C
1s, O 1s, and N 1s of the BC samples, together with cellulose reference.
The O/C ratio (0.50) in both BC samples was much lower than the theoretical value for
pure cellulose (0.83) and Whatman filter paper (0.68) or other BC values reported (Li et
al. 2009, Pertile et al. 2010, Kurniawan et al. 2012). Differences on the amount of
element components and O/C ratio could be related to the instrumental and production
methods but also to the degree of contamination. Surprisingly, N amount was increased
after the combination of alkaline purification and ultrasound treatment.
According to the high resolution C 1s data, the elevated non-cellulosic C-C component
indicate that the surface of the pristine and ultrasound-treated BC were not pure
cellulosic. This result was expected since fibril surfaces of all aqueous cellulose samples
become passivated during the drying process and the agglomeration of BC fibrils
25
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
(Österberg et al. 2013). Furthermore, increasing nitrogen together with diminishing C-C
content in the purified sample suggest that the nitrogen observed, possibly of bacterial
origin, was buried under the passivation layer and became more exposed the
purification.
Bacterial nanocellulose glycidyl methacrylate grafting.
Preparation and perspective.
Table 1: Elemental surface concentrations and relative abundance of carbon bonds of BC samples
Surface elemental composition (%)
Samples
BC
Ultra BC
Whatman
C
65.8
64.5
59.6
O
33.1
32
40.4
N
1.1
3.2
-
Na
0.3
-
Chiara Bongio, Andrea Bernardi, Marco Zarattini, Elena Vismara
Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria Chimica “G.
Natta”, Italy. [email protected]
Surface chemical groups (%)
C-C
29
26.9
3.9
C-O
54.8
54.8
75.7
C=O
14
16.4
18.6
COO
2.3
1.9
1.8
Keywords: amoxicillin, bacterial nanocellulose, drug delivery, glycidyl methacrylate
ABSTRACT
Bacterial nanocellulose (BNC) was grafted with glycidyl methacrylate (GMA) affording
BNC-GMA. Substitution degree (DS= GMA residue versus glucose unit) range in
BNC-GMA is 0.6-3. Figures 1 and 2 show NMR CP MAS spectrum of BNC and BNCGMA, respectively. As GMA grafting forms a new C-C bond between cellulose and
GMA and keeps OH cellulose groups unchanged, BNC-GMA maintains the BNC
crystallinity, see the NMR spectra. GMA appendages enhances BNC capability to
adsorb amoxicillin (A), as summarised in Table 1. GMA was further transformed to
GMAOH by opening the epoxide group with water. BNC-GMAOH adsorbs amoxicillin
(A) less than BNC-GMA, but more than BNC. It seems that the hydrophobic
appendages GMA make BNC capable to include A. Nevertheless the GMA modified
BNC can include A better than BNC. We can conclude that glycidyl methacrylate
grafting opens the way to new modified BNC suitable to develop as drug delivery
system. Figure 3 reports BNC-GMA SEM image.
Figure 1: XPS wide spectra and high resolution C 1s, O 1s and N 1s spectra of BC samples
Based on the results, BC impurities were successfully removed after the sonochemical
treatment of alkaline purified samples. Additionally, their crystallinity index and
thermal stability were increased, while surface charge was decreased. Further research
on the wettability and the surface accessibility and reactivity of the available hydroxyl
groups on the surface of these BC films will provide more useful information.
Figure 1: BNC NMR.
ACKNOWLEDGEMENTS
This work is based upon a STSM Grant from COST Action FP1205 “Innovative
applications of regenerated wood cellulose fibres”, supported by COST (European
Cooperation in Science and Technology). This work made use of Aalto University
Bioeconomy Facilities.
REFERENCES
Kurniawan, H., Laim JT. And Wang, MJ. (2012). Biofunctionalized bacterial cellulose
membranes by cold plasmas. Cellulose, 19, 1975-1988.
Li, J., Wan, Y., Li, L., Liang, H. and Wang, J. (2009). Preparation and characterization
of 2,3-dialdehyde bacterial cellulose for potential biodegradable tissue engineering
scaffolds. Materials Science and Engineering C, 29, 1635-1642.
Pertile, RAN., Andrade, FK., Alves Jr, C. and Gama, M. (2010). Surface modification
of bacterial cellulose by nitrogen-containing plasma for improved interaction with cells.
Carbohydrate Polymers, 82, 692-698.
Österberg, M., Peresin, MS., Johansson, LS. and Tammelin, T. (2013). Clean and
reactive nanostructured cellulose surface. Cellulose, 20, 983-990.
26
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
Figure 2: BNC-GMA NMR.
Preparing of nanoparticles from partly derivatized cellulose
Kay Hettrich1, Bert Volkert1
1
Fraunhofer Institute of Applied Polymer Research, Department of Biopolymer, D-14548
Potsdam, Germany. [email protected]
Keywords: cellulose derivative, etherification, nanoparticles, oxidation
ABSTRACT
Figure 3: BNC-GMA SEM.
Novel nano-scaled cellulose particles have been prepared by high-pressure
homogenizing of different pre-treated cellulose samples with Microfluidizer ™
processor (MF) in aqueous media.
One possibility of pre-treatment is the preparation of partly derivatized cellulose.
Initially cellulose derivatives with low degrees of substitution were prepared (DS > 0.5).
Afterwards nano-cellulose was obtained by a subsequent high-pressure mechanical
treatment in aqueous dispersion. Different etherification, esterification or oxidation
reactions were used for the preparation of nanoparticles in principle. The properties of
the different nanocellulose dispersion were investigated.
In order to obtain information about cellulose particle sizes, UT and MF treated
dispersions were characterized by means of static and dynamic light scattering (DLS),
ultra-centrifugation and scanning electron microscopy (SEM), rheological
measurements revealed the viscoelastic properties and gel-like structure of the materials
as well as time- and shear-dependent effects like thixotropy and pseudoplasticity
(structural viscosity).
Table 1: BNC -GMA adsorption of amoxicillin (A)
Nanocell.
time (h)
0
24
BNC-GMA
48
52
0
BNC-GMAOH
24
48
BNC
24
A/
A
A
A
mg /mg nano
0
3,72
4,27
2,53
0
1,32
0,46
0,4
In conjunction with potential applications film forming properties and temperature
dependent behaviour (e.g. viscosity) of the materials were investigated.
Selected samples of nano-cellulosic dispersions were dried via lyophilizsation, via spray
drying, and solvent exchange. The dried products were characterized in terms of
porosity (mercury porosimetry) and particle morphology (SEM). Re-dispersed samples
were compared with starting dispersions by means of SEM, DLS and rheometry.
REFERENCES
Vismara, E., Zarattini, M., Bernardi, A., Nanni, D., Bertini, S., Freire, C. Allyl, glycidyl
methacrylate and cyclodextrin-modified nanocelluloses. Preparation, characterisation
and adsorption-release specific properties. Advanced Materials TechConnect Briefs
2016, Vol. 1 Chapter 6: Nano and Microfibrillated Cellulose. Pages 172-175
28
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
Perspective use of solubilised cellulose in microbial fuel cells (MFCs)
The bacteria used in the MFC were isolated from cow gastrointestinal system that was
reported to have electrogenic activity (Inoue et al. 2013, Zheng and Nirmalakhandan
2010). The catholyte solution was 100 mM K3Fe(CN)6 in phosphate buffer. The anode
chamber was sealed with rubber stopper and the cathode chamber was in contact with
air.
Warsaw University of Life Sciences – WULS, Faculty of Wood Technology, 159
Nowoursynowska St., 02-787 Warsaw, Poland. [email protected]
Keywords: bioenergy, cellulose solubilisation, MFC
ABSTRACT
The annual biosynthesis of cellulose in the environment has been estimated on 100
million tons. This way cellulose has become the most abundant terrestrial biopolymer in
the world. Such plentiful source of carbon-rich biomass has a great potential of being an
alternative substrate for energy production. For this reason converting waste cellulosic
feedstock into energy has attracted great attention in recent years. Such process has been
realized in microbial fuel cells (MFCs). MFC technologies represent the newest
approach for generating clean energy. MFC is commonly known as bioelectrochemical
system producing current rendered by the microorganism activity. From chemical point
of view, MFC is electrochemical cell where microorganisms catalyze electrochemical
reaction (oxidation or reduction). Typical MFC is built of two electrodes: anode and
cathode placed in compartments separated by proton-exchanging membrane enabling
flow of the current between electrodes. Microorganisms are placed in the anode
compartment where they mediate in converting organic substrate into energy. As
bacteria respire, they release electrons that are transferred from the anode to the cathode
what creates electric current (Logan 2008).
Cellulose, like most biopolymers, has high energetic content, but is water insoluble
what makes it difficult substrate for energy-producing biosystems application. Naturally
occurring cellulose has crystalline structure with small amounts of amorphous regions.
The crystalline regions are resistant to bacterial enzymatic hydrolysis what eliminates it
as a carbon source for energy production in MFC systems. The problem is also
complicated by the secondary structure of cellulose e.g. monomer linkage, strands and
microfibrils.
In this work we proposed alkaline and thermal pretreatment (solubilisation) of cellulose
before its application in MFC system. Fibrous cellulose (Sigma Aldrich) 740 mg was
suspended in 20 mL of 2M NaOH solution and the mixture was shaken at room
temperature. Next, the suspension was placed at –20°C temperature until frozen. The
frozen suspension was thawed and ultrapure water was added to the sample, so that the
final concentration of cellulose in 1.3M NaOH was 2%. Subsequently, the cellulose
sample was suspended in NaOH/thiourea solution (1.5 M NaOH/0.65 M thiourea), and
the mixture was shaken at room temperature. The suspension was stored at –20°C until
frozen. After thawing, the cellulose sample was stirred to give a transparent cellulose
solution (Sugano et al 2010).
The solubilised cellulose was applied as a substrate in MFC system. The MFC was
composed of 30 ml cathode and 30 ml anode chambers separated by agar bridge (10%
agar, 10% NaCl). The anode and cathode were graphite electrodes. The anode solution
was 50 mM phosphate buffer, 1% raw cellulose or 1% solubilised cellulose.
30
The maximum power density in MFC system obtained for raw cellulose as a substrate
exceeded 18.5 mW/m2 which corresponded current density 173 mA/m2 (Fig. 1). The
operation on the solubilised cellulose caused increase in current production to
400 mA/m2 and maximum power density 28 mW/m2. Apparently, solubilisation
improved availability of cellulose to microorganisms and enzymes.
Thus, it has been shown that cellulose-rich materials, when properly treated, may be
involved in bioenergy domain and are useful substrates in biological systems for
electrical power generation.
30
raw cellulose
25
power density [mW/m2]
Renata Toczyłowska-Mamińska
cellulose solubilized
20
15
10
5
0
0
100
200
300
400
500
600
700
current density [mA/m2]
Figure 1: Polarization curves of raw and solubilised cellulose-fed MFCs.
REFERENCES
Inoue K., Ito T., Kawano Y., Iguchi A., Miyahara M., Suzuki Y., Watanabe K., (2013).
Electricity generation from cattle manure slurry by cassette-electrode microbial fuel
cells. Journal of Bioscience and Bioengineering, 116, 610–615.
Logan B.E. (2008). Microbial fuel cells. Wiley&Sons Inc. Publication, Hoboken New
Jersey
Sugano Y., Vestergaard M., Yoshikava H., Saito M., Tamiya E., (2010). Direct
electrochemical oxidation of cellulose: A cellulose-based fuel cell system.
Electroanalysis, 22, 1688-1694.
Zheng, X. and Nirmalakhandan, N. (2010) Cattle wastes as substrates for bioelectricity
production via microbial fuel cells. Biotechnology Letters, 32, 1809–1814.
31
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
COST ACTIONPoster
FP1205 BUDAPEST
22-23 September
2016
presentations
I
Spider silk-CBD-CNC composites: mechanism of assembly
Production and properties of nanocrystalline cellulose suspensions and
films
Zvi Shtein1, Sigal Meirovitch1, Shaul Lapidot2, Oded Shoseyov1
1
The Robert H. Smith Institute of Plant Sciences and Genetics in Agriculture, Robert H. Smith
Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box
2
12, Rehovot 76100, Israel Second Author Affiliation
2
Melodea Ltd. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew
University of Jerusalem, Rehovot 76100, Israel
Sebestyén Nagy, Emília Csiszár
Budapest University of Technology and Economics, Department of Physical Chemistry and
Materials Science, H-1521 Budapest, Hungary. [email protected],
[email protected]
Keywords: sonication, haze, particle size, tensile properties
Keywords: CNC, Spider silk, cellulose binding domain (CBD)
ABSTRACT
ABSTRACT
Bio-inspired material systems are derived from different living organisms such as
plants, arthropods and mammals. These biomaterial systems from nature are mostly
present in the form of composites, with molecular-scale interactions optimized to direct
functional features. Composite materials are macroscopic complexes of fibers or
particles supported by a matrix. The combination of different materials in the composite
may result in a variety of characteristics (e.g. flexibility, strength and toughness).
CNCs are most commonly extracted by sulfuric acid hydrolysis of native cellulose.
CNCs from sulfuric acid hydrolysis form stable suspensions in water due to repulsive
interactions from charged groups grafted on during hydrolysis and exhibit interesting
self-assembly, optical and mechanical properties that make them suited for a wide range
of applications.
Spider silk proteins form intrinsic composites dictated from their unique molecular
structure that combine highly crystalline domains embedded in amorphous domains
resulting in fibers that combine strength and elasticity.
The fabrication of cellulose-spider silk bio-nanocomposites comprised of CNC and
recombinant spider silk protein fused to a cellulose binding domain (CBD) is described.
Silk-CBD self-assembled to form micro-fibers and successfully bound cellulose
forming composite materials. Silk-CBD-CNC composites sponges and films shows
changes in material alignment and internal structure with the addition of silk-CBD.
.
In this research cellulose nanocrystals (CNC) were prepared from bleached cotton fibres
with sulphuric acid hydrolysis. After hydrolysis, low frequency ultrasound was applied
varying the duration of sonication to study how the length of sonication influences the
properties of CNC suspensions and those of the films prepared subsequently from the
suspensions. Changes in size of particles were followed by lased diffraction analysis
and transmission electron microscopy. For determining the surface charge of CNC, zeta
potential was measured. Stability of the suspensions was characterized by the optical
haze, which measures the percent of transmitted light that diffusely scatters. The films
prepared from the suspensions were tested by measuring the haze, oxygen transmission
rate, tensile and thermal properties (Csiszar et al. 2016).
Laser diffraction analysis and transmission electron microscopy proved that the
sonication of CNC suspensions not only disintegrated the large CNC aggregates (Dv50
14.7 μm) to individual nanowhiskers with an average length and width of 171 ± 57 and
17 ± 4 nm, respectively, but also degraded the nanocrystals and yielded shorter and
thinner particles (118 ± 45 and 13 ± nm, respectively) at 10-min sonication. The
ultrasound-assisted disintegration to nano-sized cellulose whiskers decreased the optical
haze of suspensions from 98.4 to 52.8 % with increasing the time from 0 to 10 min,
respectively. Sonication of the suspensions significantly contributed to the preparation
of films with low haze (high transparency) and excellent tensile properties. With the
increasing duration of sonication, the haze decreased (from 73.3 % to 22.2 %) and the
tensile strength rose (by 8 - 57 %) gradually. Irrespectively of sonication, however, all
films had an outstanding oxygen transmission rate in a range of 5.5 - 6.9 cm3/m2·day
and a poor thermal stability.
The best quality film with an averaged thickness of 48 μm was obtained after 10 min of
sonication and could be characterized by a haze index of 22.2 %; a tensile strength of
32.9 MPa; an elongation of 2.1 %; an oxygen transmission rate of 6.7 cm3/m2·day and a
Tonset of 203 °C.
REFERENCE
Csiszar, E., Kalic, P., Kobol, A. and Ferreira, E.P. (2016). The effect of low frequency
ultrasound on the production and properties of nanocrystalline cellulose suspensions
and films. Ultrasonics & Sonochemistry, 31, 473-480.
32
33
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
2 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
2 22-23 September 2016
Electrospun Nanofibres For Bio-Inspired Composite Materials and
Innovative Industrial Applications
Nanocellulose to Taylor the Barrier Performance of Electrospun
Biopolyester Coatings and Layers for Food Packaging
Applications
S.J. Eichhorn
College of Engineering, Maths & Physical Sciences, University of Exeter, Exeter, Devon, EX4
4QF, UK. [email protected].
Keywords: Electrospinning, nanofibres, composites
ABSTRACT
This talk will focus on both core understanding of the elecrospinning process and our
ability to control the properties of the fibres and also the applications of nanofibres
produced. Starting from fundamental models of the stochastic geometry of fibrous
networks it will be shown how a control of the fibre diameter alone can be used to tailor
pore sizes of networks. This can then be used to control the ingrowth of cells into
networks, the use of networks in composite materials and the functionality of
electrospun networks in a diverse range of applications. Following on from this it will
be shown that cellulose acetate, a readily spinnable polymer, can be used as the basis for
forming carbon fibres for electrocapacitive devices. Near field electrospinning will be
introduced as a means for patterning fibres and finally the use of template assisted
processes to make tuneable wetting surfaces, that mimic biological structures, will be
reported.
34
A. Cherpinski1, L. Cabedo2, and J.M. Lagaron1
1
Novel Materials and Nanotechnology Group, IATA-CSIC, Av. Agustin Escardino 7, Paterna
46980 (Valencia), Spain. [email protected]
ESID, University Jaume I, Castellón, Spain
2
Keywords: Nanocellulose, Electrospinning, Barrier paper, Food packaging
ABSTRACT
Electrospinning has emerged as a versatile plastic processing method to produce
nanostructured materials such as nanocomposites and nanolayers for coating
applications of paper and plastic packaging. Thanks to recent innovations in the scaling
up of this technology, industrial applications are making their way forward and may
soon become affordable for specialty applications such as barrier and active food
packaging. This presentation shows recent results where nanocellulose was used as a
filler to reinforce the barrier performance of electrospun biopolyesters such as
polyhydroxyalcanoates to be used as paper and plastic coatings. The effect of different
processing parameters and material combinations in mono and multilayer forms on the
morphology, thermal, barrier and mechanical performance will be presented here.
35
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
2 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
2 22-23 September 2016
Heterogeneous Silanization of Cellulose Nanofibers with 3Aminopropyl triethoxysilane
Cellulose in horticultural applications
Eduardo Robles, Jalel Labidi
1
1Biorefinery Processes Research Group, Chemical & Environmental Engineering Department,
University of the Basque Country UPV/EHU, Plaza Europa 1. 20018. Donostia-San Sebastian,
Spain. [email protected]
Keywords: aminopropyltrietoxysilane, cellulose nanofibers, silanization,
ABSTRACT
Abstract
The surface modification of cellulose nanofibers with 3-Aminopropyl triethoxysilane by
preserving cellulose structure and main properties was investigated. The effect of
reaction conditions, such as time and solvent types on the extent of the silanization and
fiber properties was evaluated by X-ray diffraction, thermogravimetry, 13C Nuclear
Magnetic Resonance and electronic microscopy. Surface modification with
organosilanes has been proved to be a good method to render nanocrystalline surface
hydrophobicity, giving stability to the nanocrystals (Goussé et al., 2004). Silane chains
can improve matrix-filler interactions either as suspension in organic solvents or added
as bulk into the polymeric matrix (Xu et al., 2012; Raquez et al., 2012) by serving as a
coupling agent between the cellulosic filler and the polymeric matrix. Cellulose
nanofibers were modified with 3-Aminopropyl triethoxysilane (ATS) solution inside a
plastic beaker to avoid ATS reactions with glass surface. Neat silane relation to
cellulose nanofibers was 1:1, 2.5:1 and 5:1. ATS solution was first diluted in ethanol,
ethanol-water (50/50) or water; pH was neutralized by dribbling acetic acid with
constant stirring, once pH was neutral and stable, CNF were dispersed in ethanol,
ethanol-water (50/50) or water at approximately 3 wt% and added to their
corresponding silane solution. The mixture was stirred with a Silent crusher
homogenizer at 1500 rpm during 5 min and left at room temperature for another 45 min.
The slurry was vacuum-filtered to stabilize the cellulose content and kept at 10 wt% in
the form of gel. For solid-state analysis the gel was oven cured until no humidity was
left forming thin films.
Victor Kisonen
Bio-Co / EIC Ltd., Turku, Finland
[email protected]
Keywords: Biodegradable, cellulose, horticulture, gardening, natural fibre
ABSTRACT
For being biodegradable, bio-based and abundant, the cellulose fibre well fits into the
sustainable gardening concept and the value-addition of cellulose can be considerable.
Natural fibre reinforced biodegradable composites has been a considerable area of
interest of industry (Mittal 2011). The green image increase the value of the brand and
the product. Here are some examples of lignocellulosic horticultural applications in a
market: cellulose derivative coatings in fertilisers and seeds, containers, hanging
baskets, fabrics for plant root systems and weed isolation just to name few. For instance,
lignocellulosic materials have been used to prepare biodegradable and nutritive pots for
the vegetable seedlings (Nechita at al, 2010). This technology does not produce
problematic plastic waste either. Inspired by these renewable material trends, we are
going to develop biodegradable and bio-based horticultural applications for the use of
plant nurseries, gardening retail sales and end-users.
REFERENCES
Nechita, P., Dobrin, E., Ciolocu, F., Bobu E., (2010). The biodegradability and
nutrititive pots for vegetable planting based on lignocellulose composite material.
Bio-Resources, 5, 1102-1113.
Mittal, V. (2011). Bio-nanocomposites: future high-value material. In Nanocomposites
with Biodegradable Polymers, Synthesis, Properties and Future Perspectives. Oxford
University Press.
REFERENCES
Goussé C., Chanzy H., Cerrada M.L., Fleury E. (2004). Suface silylation of cellulose
microfibrils: preparation and rheological properties, Polymer, 45, 1569-1575.
Xu S.H., Gu J., Luo Y. F., Jia D. M. (2012). Effects of partial replacement of silica with
surface modified nanocrystalline cellulose on properties of natural rubber
nanocomposites, Express Polymer Letters Vol. 6, No. 1, 14-25.
Raquez J. M., Murena Y., Goffin A. L., Habibi Y., Ruelle B., DeBuyl F., Dubois P.,
(2012). Surface modification of cellulose nanocrystals and their use as nanoreinfocers
into polylactide: A sustainably-integrated approach, Composites Science and
Technology, 72 544-549.
36
37
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
Cellulose nanofibers from industrial residues and their use in
composite materials
Herrera N, Roch H, Salaberria A M, Pino M A, Labidi J, Fernandes SCM, Radic D,
Leiva A, Oksman K. (2016) Functionalized blown films of plasticized polylactic/chitin
nanocomposite: preparation and characterization, Materials Design 92 846-852.
Kristiina Oksman1,2
Luleå University of Technology, Division of Materials Science, SE-97187 Luleå, Sweden
1
[email protected]
2
University of Oulu, Fiber and Particle Engineering, Oulu, Finland
Keywords: Applications, cellulose nanofibers, energy consumption, grinding process,
nanocomposites processing, spinning, foaming, extrusion.
ABSTRACT
The presentation will introduce the audiences on production of cellulose nanofibers and
nanocomposites, also their properties and some possible applications will be discussed.
Cellulose nanocomposites have been very popular research subject during the last 15
years and many studies have been made on the development of these materials.
Nanocelluloses can be prepared using mechanical and chemical methods. We are
working with Masuko ultrafine grinding process and separation of industrial residues to
nanosize cellulose and focussing on energy consumption and yield. The viscosity,
optical microscopy images and mechanical properties are usually evaluated to follow
the fibrillation process. X-ray diffraction (XRD) and Raman spectroscopy can be used
to reveal that the materials are isolated without affecting their crystallinity. We have
shown that a residue from carrot juice process is very easily bleached and consumes less
energy during grinding process compared with common pulp. Moreover, dried
nanofiber networks from carrot showed high mechanical properties, with an average
modulus and strength of 12.9 GPa and 210 MPa respectively, thus indicating a
homogeneous nanosize distribution. We believe that residues such as carrot have great
potential for the industrial production of cellulose nanofibers because of the processing
efficiency combined with low raw material cost. (Siqueira et al 2016, Berglund et al
2016)
Processing methods such as foaming, solvent casting, resin impregnation, fiber spinning
and extrusion of cellulose nanocomposites are currently of great interest and will be
discussed. Addition of nanocellulose into the polymer matrix do not only improve the
mechanical properties of the composite but can add new functionalities for the polymer
but one of the difficulties, when producing cellulose-based nanocomposites, is to
disperse the nanocellulose in the polymer matrix without degradation the polymer or the
nanocellulose. Pros and cons are as well as future application are shown. (Aitomäki et al
2016, Herrera et al 2016, Hooshmand et al 2015, Oksman et al 2016, Zhou et al 2016,
Siqueira et al 2016)
Hooshmand S, Aitomäki Y, Norberg N, Mathew AP and Oksman K. (2015) Dry spun
single filament fibers using only cellulose nanofibers from bio-residue, ACS Applied
Materials and Interfaces 7 (23) 13022-13028.
Oksman K, Aitomäki Y, Mathew AP, Siqueira G, Zhou Q, Butylina S, Tanpichai S,
Zhou X, Hooshmand S. (2016) Review of the recent developments in cellulose
nanocomposite processing, Composites part A 83 2-18.
Siqueira G, Tadokoro S K, Mathew AP, Oksman K, (2016) Re-dispersible carrot
nanofibers with high mechanical properties separated from juice residue, Comp Sci
Technol 12349-56.
Zhou X, Sethi J, Berglund L, Aitomäki Y, Frisk N, Sain MM, Oksman K. (2016)
Dispersion and reinforcing effect of carrot nanofibers on biopolyurethane foams.
Materials Design 110 526-531
REFERENCES
Berglund L, Noël M, Aitomäki Y, Öman T, Oksman K. (2016) Production potential of
cellulose nanofibers from industrial residues: efficiency and nanofiber characteristics,
Ind Crops Prod 92, 84-92.
38
39
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
Hydrophobic nanocellulose-based aerogels for selective oil
removal: an effective and simple method
shows the evolution of the contact angle as the amount of AKD was increased for the
three types of CNF selected. As it can be seen, the water contact angle was increased as
the amount of AKD was too. Apparently, the use of the obtained aerogels shows a
strong and environmentally friendly alternative for oil removal in the high seas.
Quim Tarrés, Helena Oliver-Ortega, Miquel Llop, M. Àngels Pèlach,
Marc Delgado-Aguilar, Pere Mutjé
University of Girona, LEPAMAP research group, C/ Maria Aurèlia Capmany, 61, Girona
(17003), Spain.
[email protected]
Keywords: aerogels, alkyl ketene dimer, cellulose nanofibers, oil removal
ABSTRACT
Nowadays, several methods are being used such as the collection of the oil on water
surface (taking advantage of their different densities), dispersing oil in water promoting
its natural degradation or in situ burning (Korhonen et al. 2011). Often, depending on
the sensitiveness of the area, unfortunately the best option is to watch and wait for
natural attenuation. None of the abovementioned methodologies seem to be quite
efficient or environment-friendly. Many efforts have been performed to overcome this
situation, such as depositing sawdust on water-oil mix surface with the purpose of
removing the hydrophobic component. However, sawdust also absorbs water, which
makes quite difficult its reuse (Nordvik et al. 1996).
Cellulose nanofibers (CNF) have become one of the main topics of research for
cellulose and polymer scientists and technicians. Aerogels made of CNF are a product
of interest due to their lightweight, great specific surface and, thus, their huge porosity.
Even they have been considered in the colloquial jargon as “solid smoke”. Moreover,
aerogels made of CNF present great mechanical properties (Zhang et al. 2014, Ayadi et
al. 2016), fact that confers them a good dimensional stability. CNF, in its native form,
have a huge hydrophilic character (even greater than the abovementioned sawdust),
what would make also difficult their use for oil removal. In this sense, chemical
modification of CNF is also in a growing stage, mainly focused on the
hydrophobization of their surface (Korhonen et al. 2011). There is some literature
available where CNF are modified through silanation (Aulin et al. 2010) techniques and
acetylation. The main drawback of these methods is the use of organic solvents, which
at first sight, makes difficult their implementation at large scale mainly due to the strict
safety regulations that these products force to adopt.
In this sense, aerogels made of cellulose nanofibers from bleached kraft hardwood pulp
will be developed by three well differentiated methodologies: TEMPO-mediated
oxidation (Saito et al. 2007), enzymatic hydrolysis (Tarrés et al. 2016) and mechanical
methods (Delgado-Aguilar et al. 2015). In addition, before preparing the aerogels, the
obtained CNF will be properly modified by the addition of AKD, ranging the dosage
between 0 to 10% and they will be submitted to some static and dynamic tests in order
to determine the feasibility of using them as selective oil removers, as well as their
capability to be used more than once (recycling tests).
The visual aspect of the obtained aerogels was similar regardless the type of CNF used,
as well as the added amount of AKD. Those aerogels modified with AKD presented, at
first sight, a high water contact angle, which was quantified during aerogels
characterization for each type of CNF and each modification degree. The water drops
behaviour on aerogels surface can be observed in Fig. 1. On the other hand, Fig.1 also
40
Figure 1: Evolution of the contact angle as the amount of AKD is increased
REFERENCES
Aulin, C., Netrval, J., Wågberg, L. and Lindström, T. (2010). Aerogels from
nanofibrillated cellulose with tunable oleophobicity. Soft Matter, 6(14), 3298-3305.
Ayadi, F., Martín-García, B., Colombo, M., Polovitsyn, A., Scarpellini, A., Ceseracciu,
L., Moreels, I. and Athanassiou, A. (2016). Mechanically flexible and optically
transparent three-dimensional nanofibrous amorphous aerocellulose. Carbohydrate
Polymers,
Delgado-Aguilar, M., Tovar, I. G., Tarrés, Q., Alcalá, M., Pèlach, M. À. and Mutjé, P.
(2015). Approaching a Low-Cost Production of Cellulose Nanofibers for Papermaking
Applications. BioResources, 10(3), 5345-5355.
Korhonen, J. T., Kettunen, M., Ras, R. H. and Ikkala, O. (2011). Hydrophobic
nanocellulose aerogels as floating, sustainable, reusable, and recyclable oil absorbents.
ACS applied materials & interfaces, 3(6), 1813-1816.
Nordvik, A. B., Simmons, J. L., Bitting, K. R., Lewis, A. and Strøm-Kristiansen, T.
(1996). Oil and water separation in marine oil spill clean-up operations. Spill Science &
Technology Bulletin, 3(3), 107-122.
Saito, T., Kimura, S., Nishiyama, Y. and Isogai, A. (2007). Cellulose nanofibers
prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules, 8(8),
2485-2491.
Tarrés, Q., Saguer, E., Pèlach, M. A., Alcalà, M., Delgado-Aguilar, M. and Mutjé, P.
(2016). The feasibility of incorporating cellulose micro/nanofibers in papermaking
processes: the relevance of enzymatic hydrolysis. Cellulose, 23(2), 1433-1445.
hang, ., Sèbe, G., Rentsch, D., Zimmermann, T. and Tingaut, P. (2014).
Ultralightweight and flexible silylated nanocellulose sponges for the selective removal
of oil from water. Chemistry of Materials, 26(8), 2659-2668.
41
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
Preliminary results of the application of carboxymethylated cellulose as
a reinforcing agent in papermaking
Helena Oliver-Ortega1, Quim Tarrés1, Maria Àngels Pèlach1, Manel
Alcalà2, Marc Delgado-Aguilar1, Pere Mutjé1.
Table 1: Preliminary results in length rupture, tensile index and Schopper-Riegler
degree of CMC addition in virgin fibres with a mechanical beating and in recycled
fibres.
BL (m)*
Tensile
index
(N·m/g)
*
BL at
pope
(m)**
7,582
74.3
10,737
3,670
6,640
1
University of Girona, Group LEPAMAP, Department of Chemical Engineering, C/M. Aurèlia
Capmany, nº61, 17003 Girona, Spain. [email protected]
2
University of Girona, Design, Development and Product Innovation, Dpt. of Organization,
Business Management and Product Design, C/M. Aurèlia Capmany, nº61, 17003 Girona, Spain
Keywords: Carboxymethylated Cellulose (CMC), Papermaking, Recycled Fibres,
Sustanability.
ABSTRACT
Today, one of the main problems of papermaking industry is, as professor Martin
Hubbe reported in a recent review, that “paper production requires large amounts of
cellulosic fibre, whereas the world’s forested lands and croplands have a finite capacity
to supply such resources” (Hubbe, 2014). In order to reduce this dependence from
virgin fibres, the use of recycled fibres is being considerably increased. Actually, the
80% of the fibers used for paper production in Spain come from recovered papers.
However, during paper recycling, fibers experience mechanical properties losses due to
shear and friction forces, as well as hornification phenomena. In order to successfully
recover the original paper properties, papermakers usually include mechanical refining
in their paper production processes; nonetheless, it is well known that mechanical
refining causes permanent and irreversible structural damages to fibers which
considerably reduces fibers’ lifespan (Delgado-Aguilar, Tarrés, Pèlach, Mutjé, &
Fullana-i-Palmer, 2015). In this sense, chemical-based strategies are gaining importance
in papermaking research due to their lower side-effects on paper slurries. Among them,
cellulose nanofibers as a reinforcing agent deserve special attention (Delgado-aguilar,
González, Tarrés, Alcalà, & Pèlach, 2015; Tarrés et al., 2016). However, the efficiency
of the cellulose nanofibres is reduced when they are used in mechanically refined fibres
and also with recycled fibres.
Another alternative is the use of carboxymethylated cellulose (CMC). While CMC is
currently used in papermaking industries, it is usually as an ionic agent to control the
high conductivity of the water, not for mechanical properties of paper enhancement.
Some previous works showed significant increments in the mechanical propertites of
the papers by the addition of CMC (Aarne, Kontturi, & Laine, 2012; Fras Zemljic,
Stenius, Laine, & Stana-Kleinschek, 2008), although the reinforcing mechanism of
CMC is still being investigated (Ankerfors, Duker, & Lindström, 2013).
LEPAMAP group (University of Girona, Spain) has recently started to study the use of
CMC as a reinforcing agent in papermaking. The addition of a moderate amount in two
different fibres (virgin hardwood fibres and recycled fibres from newspapers and
magazines) has shown really optimistic results (Table 1).
The results shown above induce to consider the use of CMC as an alternative
reinforcing agent in papermaking processes, leading the obtained papers to be used for
high-performance applications or to implement several environmental friendly strategies
such as reducing basis weights of papers or further increasing the amount of mineral
fillers (i.e. PCC).
42
Virgin fibres + mechanical refining
Virgin fibres + mechanical refining
+ CMC
Recycled fibres
Recycled fibres + CMC
ᵒSR
ΔBL (%)
10,614
32
-
105.3
15,032
37
41.6
36.0
65.1
5,138
9,296
40
60
80.9
BL: breaking length
*Isotropic sheet former
**An anisotropy ratio of 1.4 has been applied (Delgado-Aguilar, Tarrés, Puig, et al.,
2015)
REFERENCES
Aarne, N., Kontturi, E., & Laine, J. (2012). Carboxymethyl cellulose on a fiber
substrate: The interactions with cationic polyelectrolytes. Cellulose, 19(6), 2217–
2231. http://doi.org/10.1007/s10570-012-9793-2
Ankerfors, M., Duker, E., & Lindström, T. (2013). Topo-chemical modification of
fibres by grafting of carboxymethyl cellulose in pilot scale. Nordic Pulp and Paper
Research Journal, 28(1), 6–14.
Delgado-aguilar, M., González, I., Tarrés, Q., Alcalà, M., & Pèlach, M. À. (2015).
Approaching a Low-Cost Production of Cellulose Nanofibers for Papermaking
Applications, 10(3), 5345–5355.
Delgado-Aguilar, M., Tarrés, Q., Pèlach, M. A., Mutjé, P., & Fullana-i-Palmer, P.
(2015). Are Cellulose Nanofibers a Solution for a More Circular Economy of
Paper Products? Environmental Science and Technology, 49(20), 12206–12213.
Delgado-Aguilar, M., Tarrés, Q., Puig, J., Boufi, S., Blanco, A., & Mutjé, P. (2015).
Enzymatic Refining and Cellulose Nanofiber Addition in Papermaking Processes
from Recycled and Deinked. BioResources, 4, 5730–5743.
Fras Zemljic, L., Stenius, P., Laine, J., & Stana-Kleinschek, K. (2008). Topochemical
modification of cotton fibres with carboxymethyl cellulose. Cellulose, 15(2), 315–
321. http://doi.org/10.1007/s10570-007-9175-3
Hubbe, M. A. (2014). Prospects for maintaining strength of paper and paperboard
products while using less forest resources: A review. BioResources, 9(1), 1634–
1763.
Tarrés, Q., Saguer, E., Pèlach, M. A., Alcalà, M., Delgado-Aguilar, M., & Mutjé, P.
(2016). The feasibility of incorporating cellulose micro/nanofibers in papermaking
processes:
the
relevance
of
enzymatic
hydrolysis.
Cellulose.
http://doi.org/10.1007/s10570-016-0889-y
43
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
COST ACTION FP1205 SESSION
BUDAPEST
3 22-23 September 2016
Relevance of retention systems when using cellulose nanofibers as
strength additives in papermaking
drained water on real time. Solids retention was also measured. Z-potential was
measured in a ZetaPlus unit from Brookhaven Instruments (Holtsville, USA).
Handsheets were prepared in a normalized (ISO 5269/2, DIN 54 358) sheet former
Rapid-Köthen from PTI (Vorchdorf, Austria). These handsheets were conditioned in a
weather chamber at 25 ºC and 50% humidity for 24 h before physical and mechanical
tests were performed by using an AUTOLINE 300 from Lorentzen & Wettre
(Stockholm, Sweden). The quality of the sheets formation was measured in a Beta
formation tester from Ambertec (Espoo Finland).
Noemi Merayo, Ana Balea, Elena de la Fuente, Ángeles Blanco,
Carlos Negro
1
Complutense University of Madrid, Department of Chemical Engineering, Avda. Complutense
s/n 28040 Madrid, Spain. [email protected]
Keywords: cellulose nanofibers, drainage process, papermaking, paper strength,
retention systems.
ABSTRACT
Cellulose nanofibers (CNF) have been successfully applied to increase paper strength
(Balea et al. 2016a; Gonzalez et al. 2012; Petroudy et al. 2014). Moreover, CNF can
reduce linting tendency during printing (Balea et al. 2016b) and provide especial
properties to the paper, such as low porosity (Eriksen et al. 2008) or smoothness (Osong
et al. 2016). CNF retention in the paper web is an important issue to consider, which is
join to dewatering difficulties, and this is one of the important drawbacks for the
implementation of CNF at industrial scale (Osong et al. 2016). During papermaking,
retention systems are commonly used to assure retention of fines and fillers during the
drainage step. In the case of CNF, a retention agent is also used, being cationic starch
very common. In this research, several retention systems have been used in combination
with CNF trying to avoid dewatering difficulties, but favouring CNF retention.
Pulp was prepared through disintegration of 20 g of dry 100% recovered paper (60%
old newspaper and 40% old magazine without inks) by using a Messmer pulp
disintegrator (Mavis Engineering Ltd, London) at 180000 revolutions and 1 wt%
consistency. CNF was obtained from never dried refined Eucalyptus globulus ECF
bleached kraft pulp (EBK), with a Canadian Standard Freeness (CSF) of 540.8 mL,
produced by Torraspapel S.A. in Zaragoza, Spain. Nanofibrillated material was obtained
by TEMPO mediated oxidation, by using 5 mmol of NaClO per gram of EBK pulp
(Saito et al. 2007), cleaning process through several cycles of dilution and filtration and
six steps of homogenization at 600 bar in a laboratory homogenizer PANDA PLUS
2000 manufactured by GEA Niro Soavi (Parma, Italy). Five different retention systems
(RS) were assessed in this study:
(1) C-PAM formed by low molecular weight coagulant and high molecular
weight polyacrylamide (PAM) (NALCO, Naperville, USA).
(2) C-PAM-B formed by high molecular weight coagulant, high molecular
weight PAM and hydrated bentonite clay (BASF, Ludwigshafen, Germany).
(3) Chitosan (CH) of low molecular weight (PANREAC, Barcelona, Spain).
(4) Cationic starch (CS) with degree of substitution of 0.02-0.17 (SOLAM,
Emlichheim, Germany)
(5) Polyvinylamine (PVA) of high molecular weight (BASF, Ludwigshafen,
Germany).
Results obtained in this research show that addition of CNF not always implies
difficulties during the drainage process because behaviour during dranage depends
strongly on the RS used. Moreover, CNF could contribute to solve the contradiction
between the improvement in drainage rate and the improvement in sheet formation and
mechanical properties. The use of CH as RS resulted in sheets with the highest values of
TI, these values increased by using CNF. The use of 1% CNF is enough to revert the
effect of using the C-PAM-B RS on the TI without affecting the drainage rate. Although
the use of CNF and low doses of CS improves the TI of the paper, when the dose of CS
used is that required to increase drainage rate, the high interaction between CS and CNF
reduces the TI of the sheet.
REFERENCES
Balea, A., Blanco, A., Merayo, N. and Negro, C. (2016b). Effect of nanofibrillated
cellulose to reduce linting on high filler-loaded recycled papers. Appita Journal, 69,
148-156.
Balea, A., Merayo, N., Fuente, E., Delgado-Aguilar, M., Mutje, P., Blanco, A. and
Negro, C. (2016a). Valorization of corn stalk by the production of cellulose nanofibers
to improve recycled paper properties. Bioresources, 11, 3416-3431.
Eriksen, O., Syverud, K. and Gregersen, O. (2008). The use of microfibrillated cellulose
produced from kraft pulp as strength enhancer in TMP paper. Nordic Pulp and Paper
Research Journal, 23, 299-304.
González, I., Boufi, S., Pèlach, M.A., Alcalà, M., Vilaseca, F. and Mutjé, P. (2012).
Nanofibrillated cellulose as paper additive in eucalyptus pulps. BioResources, 7, 51675180.
Osong, S.H., Norgren, S. and Engstrand, P. (2016). Processing of wood-based
microfibrillated cellulose and nanofibrillated cellulose, and applications relating to
papermaking: a review. Cellulose, 23, 93–123.
Petroudy, S.R.D., Syverud, K., Chinga-Carrasco, G., Ghasemain, A. and Resalati, H.
(2014). Effects of bagasse microfibrillated cellulose and cationic polyacrylamide on key
properties of bagasse paper. Carbohydrate Polymers, 99, 311-318.
Saito, T., Kimura, S., Nishiyama, Y. and Isogai, A. (2007). Cellulose nanofibers
prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules, 8,
2485-2491.
Drainage measurements were performed in a MütekTM DFR-05 from BTG Instruments
(Säffle, Sweden), which provides drainage curves of the pulp when it is drained by
gravity through 250 mesh. The program was monitoring and recording the weight of the
44
45
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTION FP1205 BUDAPEST 22-23 September 2016
COST ACTIONPoster
FP1205 presentations
BUDAPEST 22-23 September
2016
II
COST ACTIONPoster
FP1205 presentations
BUDAPEST 22-23 September
2016
II
Synthesis and characterisation of nanocellulose aerogels for the
elaboration of innovative biosourced bone substitutes.
100% recycled paper packaging materials: processing, properties and
potential application
Benjamin Dhuiège1, Laurent Plawinski,2 Marie-Christine Durrieu,2
Gilles Sèbe1,3
Laura Vikele, Linda Rozenberga, Inese Sable, Marite Skute, Linda
Vecbiskena, Uldis Grinfelds, Juris Zoldners, Anrijs Verovkins, Rita
Treimane
1
CNRS, LCPO, UMR 5629, F-33607 Pessac, France
2
CNRS, CBMN, UMR 5248, F-33607, Pessac, France
Latvian State Institute of Wood Chemistry, 27 Dzerbenes Street, Riga, Latvia, LV-1006.
[email protected]
3
University of Bordeaux, LCPO, UMR 5629, F-33607, Pessac, France
Keywords: chitosan, moulded fibre, packaging, recycled paper
[email protected]
ABSTRACT
Keywords: nanocellulose aerogels, biosourced scaffolds, innovative bone substitute
ABSTRACT
Nanofibrillated cellulose (NFC) is a nanomaterial composed of long, flexible and
interconnected cellulose nanofibers, which can be produced by mechanical
disintegration of cellulose substrates such as microcrystalline cellulose, paper or pulp.
Because of its biocompatibility, excellent mechanical properties and renewability, this
nanocellulose is increasingly considered as nanoscale building block for the elaboration
of innovative materials, including biomedical materials (Tingaut et al. 2012, Lin and
Dufresne 2014). In particular, NFC has the potential to serve as tissue bioscaffold by
providing a cell-friendly environment to encourage the attachment and proliferation of
cells (Lin and Dufresne 2014).
In a recent work, we showed that flexible and ultralightweight nanocellulose aerogels
with tunable properties could be prepared by a simple silylation method in water with
alkoxysilanes (Zhang et al. 2014). Therefore, here we report on the synthesis of silylated
NFC aerogels to be used as biosourced scaffold for the regeneration of bone tissues.
Various silylated aerogels with different surface properties were synthesized in different
conditions and characterized with regards to their chemistry, morphology, thermal
stability and mechanical properties. The impact of the aerogels properties on the
adhesion and the differentiation of Human mesenchymal stem cells will be later
investigated in view of a potential application as bone substitute material.
Tingaut, P., Zimmermann, T. and Sebe, G. (2012) Cellulose nanocrystals and
microfibrillated cellulose as building blocks for the design of hierarchical functional
materials. Journal of Materials Chemistry, 22, 20105-20111.
Lin, N. and Dufresne, A. (2014) Nanocellulose in biomedicine: current status and future
prospect. European Polymer Journal, 59, 302-325.
Zhang, Z., Sèbe, G., Rentsch, D., Zimmermann, T. and Tingaut, P. (2014)
Ultralightweight and flexible silylated nanocellulose sponges for the selective removal
of oil from water. Chemistry of Materials, 26, 2659-2668.
Every year several hundred million tons of paper are produced. Production in 2013
amounted to 402.6 million tons, which is 57 kg of paper per person (The Statistic Portal
2016). The industry has rapidly switched to production of packaging materials made of
paper: 47.5% – packaging material, 40.5% – office paper, 7.7% – hygiene paper, and
4.3% – special paper, such as money or securities (Confederation of European Paper
Industry 2016). Environmentally friendly packaging materials can save the World;
especially, usage of reusable, recyclable and biodegradable packaging materials.
Nowadays, the packaging manufacturing companies are offering environmentally
friendly materials with a high proportion of recycled paper.
This research is focused on making eco-friendly packaging materials using 100%
recycled paper – recycled newspapers, magazines, carton boxes and office papers
(V.L.T. Ltd, Latvia). In this work, the influence of natural additive – chitosan (medium
molecular weight with a deacetylation degree of 70%) – on physical–mechanical
properties, air permeability, antimicrobial properties and biodegradability of recycled
paper packaging materials was investigated. The mechanical properties were evaluated
using FRANK Tensile Tester (DIN EN ISO 1924-1 standard), but the air permeability
was detected using L&W Air Permeance Tester. Recycled paper packaging materials
were assessed against Staphylococcus aureus (S. Aureus ATCC 25923, gram-positive)
and Escherichia coli (E. Coli ATCC 25922, gram-negative) as model bacteria by
inhibition zone formation, and composted up to 40 days.
The results showed that the obtained prototype of an egg box has better mechanical and
wet strength properties than the analogues available on the market (Table 1). The
additive of the chitosan solution does not affect significantly the air permeability of the
sample.
Table 1: Physical-mechanical properties and air permeability of the prototype
and the analogues available on the market.
Tensile index, Nm g–1
Air permeability, ml
Grammage,
Sample
–2
min–1
gm
Dry
Wet
428 ± 7
3.5 ± 0.2
2.52 ± 0.13
610 ± 12
A
593 ± 9
5.41 ± 0.13
0.43 ± 0.08
635 ± 21
B
455 ± 4
3.3 ± 0.3
2.3 ± 0.2
628 ± 14
C
514 ± 6
6.3 ± 0.4
3.8 ± 0.3
630 ± 17
Prototype
The results of antibacterial tests confirmed that prototype of an egg box inhibited the
growth and development of S. aureus and E. coli; the stronger antimicrobial properties
to E. coli culture comparing to S. aureus culture. Other eggs boxes, analogues available
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on the market (A, B and C) showed no antimicrobial efficiency. The gravimetric test
results showed (Table 2) that after 5 days in compost the samples of egg boxes have
composed by 10%, after 10 and 15 days – by 20–30%, after 20 days – by 40–42%, after
25 days – more than 50%, after 30 days – by 65–70%, and after 35 days – by 80–85%.
Cellulose-based controlled-release agrochemicals formulation.
Table 2: The gravimetric evaluation of biodegradability of the prototype
and the analogues available on the market.
Weight loss, %
Sample
5 days
10 days
15 days
20 days
25 days
30 days
35 days
9
20
32
42.5
55
69
84
A
11.5
21.5
34
43
50
65.5
79.5
B
8.5
19
30
40.5
50
71
85
Prototype
Alena Šišková1, Piotr Rychter2, Andrej Opálek3, William Porzio4,
Angela Kleinová1, Ivica Janigová1, Anita Eckstein Andicsová1
1
Polymer Institute SAS, Dúbravská cesta 9, 84541 Bratislava, Slovakia;
[email protected], anita.andicsova@savba,sk
Jan Długosz University, Institute of Chemistry, Environment Protection and Biotechnology
42-200 Czestochowa, Armii Krajowej 13/15. Poland;
2
Institute of Materials and Machine Mechanics SAS, Dúbravská cesta 9, 84513 Bratislava,
Slovakia;
3
In addition, after 40 days the degree of the degradability was near to 95–100%; it was
not possible to separate precisely from compost all the undecomposed small parts of the
sample, therefore the degradability was observed visually. No significant differences
between the prototype and the analogues currently available on the market have been
discovered.
A prototype of a moulded fibre paper material with the chitosan additive has been
developed and its properties in comparison with the analogues existing on the market –
determined. The mechanical strength of the prototype exceeds by approximately 20%
comparing to the analogues and the wet strength of the prototype – by approximately
50%; besides the prototype shows antimicrobial properties, and it decomposes in
40 days.
Acknowledgments: This research has been supported by the European Regional
Devel
e Fu d w h he r je “I ve ga
f e fr e dly
lded a er f bre
a er al f r u e f f d a k g w h add ve fr
re ewable re ur e ”, No.
2DP/2.1.1.1.0/14/APIA/VIAA/042.
REFERENCES
Confederation of European Paper Industry, http://www.cepi.org/node/19364
(seen 19.02.2016.). Production of paper and board in Europe in full transformation.
The Statistic Portal, http://www.statista.com/statistics/270314/production-of-paper-andcardboard-in-selected-countries/ (seen 19.01.2016.). Production volume of paper and
cardboard worldwide 2006 to 2013.
48
4
Institute of Macromolecular Chemistry CNR, E. Bassini 15, 20133 Milano, Italy.
Keywords: cellulose, chemical modifications, click reaction, controlled release
systems, pesticides.
ABSTRACT
Because of the increasing contamination of groundwater and soil caused by human
agriculture activity, especially by treatment of crops by harmful substances, there are
the growing demands for systems of controlled release of agrochemicals. The main
objective of this research is to design, prepare and characterize the material suitable for
controlled release system for potential use in agri- and horti-culture.
This study involving the preparation of films/fibrous mats as suitable polymer carrier
for pesticides and subsequently immobilization of that plant protection chemicals what
will contribute to the decrease of pesticides mobility and its leaching into the
groundwater and the soil (Dubey et al. 2011).
Natural polymer/pesticide form allows prolonged release of the active agent and
simultaneous degradation of the polymer carrier. From natural polymers the cellulose is
the most abundant material in the world and in the intended process the secondary raw
cellulosic material from the waste can be used. As a model pesticide was selected
metribuzin. It is herbicide widely used in agriculture. It acts by inhibiting
photosynthesis by disrupting photosystem II. It has been found that it contaminated
groundwater (Roberts and Hutson 1998).
Several approaches to the modification of cellulose were studied.
The surface modification of cellulose films/fibrous mats and simultaneously the
chemical modification of cellulose in solution were carried out by specific “click”
reaction (Figure 1). The modified materials were characterized by various methods such
as SEM, FTIR, XRD, EAI and by thermal analysis. We were looking for clear-cut
evidence of the occurrence of chemical reactions on hydroxyl functions of cellulose.
This work was supported by the Slovak Grant Agency VEGA project No. 2/0142/14, by
Slovak Research and Development Agency, project No. APVV 15-0528 as well as by
COST FP 1205.
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Influence of the particle concentration and Marangoni flow on
the formation of cellulose nanocrystal films
Alican Gençer, Christina Schütz, Wim Thielemans
Renewable Materials and Nanotechnology Group, Department of Chemical Engineering,
KU Leuven, Campus Kulak Kortrijk, Etienne Sabbelaan 53, 8500 Kortrijk, Belgium
[email protected]
Cellulose substrate
Figure 1: Process of specific “click” reaction Cu (I) – catalyzed azide – alkyne
cycloaddition.
Keywords: colloidal stability, Marangoni flow, optical properties
ABSTRACT
REFERENCES
Dubey. S., Jhelum, V. and Patanjal P.K. (2011). Controlled release agrochemical
formulations: A review. Journal of Scientific & Industrial Research, 70, 105-112.
Roberts, T.R., Hutson, D.H. (1998). Metabolic Pathways of Agrochemicals: Herbicides
and plant growth regulators. Royal Society of Chemistry, Thomas Graham House,
Cambridge, 1998.
Cellulose nanocrystals, rod-like crystalline nanoparticles are a bio-based material that
can be a great alternative to obtain films with tunable optical properties. Iridescent and
light diffracting films can readily be obtained via the drying of a suspension of cellulose
nanocrystals.(Lagerwall et al., 2014) This deposition of the particles together with the
self-assembly in the suspension has a direct effect on the optical properties of obtained
films. The particle deposition onto a substrate is affected by the flow dynamics inside
sessile droplets which usually yields a ring-shaped deposition pattern.(Deegan et al.,
1997) We thus set out to investigate the deposition process and to control it in order to
be able to generate the desired deposition pattern. To do this, we controlled the
deposition patterns of the cellulose nanocrystal films by drying the films in different
environments. We could thus obtain iridescent films with a uniform thickness by
exerting control over the relative magnitude of the Marangoni flow and the colloidal
stability of cellulose nanocrystal dispersions.
Figure 1 Photographs of cellulose nanocrystal films and uniform deposition by the means of
Marangoni flow
REFERENCES
Lagerwall, J. P. F., Schutz, C., Salajkova, M., Noh, J., Hyun Park, J., Scalia, G., &
Bergstrom, L. (2014). Cellulose nanocrystal-based materials: from liquid crystal selfassembly and glass formation to multifunctional thin films. NPG Asia Mater, 6, e80.
Deegan, R. D., Bakajin, O., Dupont, T. F., Huber, G., Nagel, S. R., & Witten, T. A.
(1997). Capillary flow as the cause of ring stains from dried liquid drops. Nature,
389(6653), 827-829.
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Bio-based foams from renewable and sustainable polyols obtained by
liquefaction of lignocellulosics
kept under 33% to avoid the recondensation reactions The strong hydrogen bonding
contained in lignocellulosics is a result of the large number of hydroxyl groups present
in the molecular chains of biopolymers. During liquefaction process, the polyhydric
alcohols and acid catalysts lead the disrupting hydrogen bonding with additional
hydroxyl groups to struggle with the cellulose inter- and intra-chain hydrogen hydrogen
bonding and their large size impels the chains apart. This phenomena reduce the
efficiency of the process causing recondensation reaction (Yaoguang et al. 1996).
Tufan Salan1, M. Hakkı Alma2
1
Kahramanmaras Sutcu Imam University, Department of Materials Science and Engineering,
Avsar Campus, 46100, Kahramanmaras, Turkey. [email protected]
2
Kahramanmaras Sutcu Imam University, Department of Forest Industry Engineering, Avsar
Campus, 46100, Kahramanmaras, Turkey. [email protected]
Keywords: Bio-polyols, foam, lignocellulosic biomass, liquefaction
ABSTRACT
Foams are one of the most useful three dimensional materials with great versatility
because they can be used in various forms in several applications areas such as
packaging, cushioning and insulation. Polymeric foams involve polyurethane foam
(PUF), polystyrene foam (PSF) and phenolic foam (PF). The production of these
materials consist of varied processing conditions such as gaseous extrusion of molten
polystyrene (PS) into foam while the reaction of selected polyols (polyether and
polyester) and isocyanate with a blowing agent generate PUF. On the other hand, the PF
manufacturing procedure needs the usage of a heat/acid reactive resole type phenolic
resin, emulsifier, a volatile blowing agent and an acid catalyst (Pilato 2010). The major
drawback of these petroleum-based foams is that they are typically manufactured from
non-renewable, non-recyclable and not-biodegradable raw materials. Accordingly, due
to increasing concerns about fossil sources lignocellulosics has become an attractive
alternative for the production of bio-based materials.
Lignocellulosics such as agricultural and forestry wastes naturally involve bio-polymers
such as cellulose, hemicellulose, lignin and tannin which contain more than one
hydroxyl group in the molecular chains. The liquefaction method is an effective way to
convert lignocellulosic feedstock into intermediate bio-polyols which can be used as a
starting raw material for the production of green polymers. Liquefaction of
lignocellulosic biomass in the presence of organic solvents became a popular research
area over the last decade. The polyhydric alcohols and phenol are the most used
solvents while different organic solvents have been used in liquefaction reaction. So far,
the liquid products obtained after liquefaction of biomass have been applied to
preparation of novolak and resol type phenolic resins, Bakelite like molding materials,
carbon fibers, polyesters, epoxy resins, resol type PF and PUF.
It has been proven by many scientists that the liquefied biomass obtained using
polyhydric alcohols such as polyethylene glycol (PEG), glycerol or their mixtures as
liquefaction solvents could be used directly as polyols for the manufacturing of PUFs
without additional treatment. These foams were produced in three different structures
comprised the rigid type using polymeric methylene diphenylene diisocyanate (PMDI)
(Alma and Basurk 2003), semi-rigid type using polyaryl polymethylene isocyanate
(PAPI) (Gao et al. 2010), and flexible type using toluene diisocyanate (TDI) (Zhang et
al. 2012). Polyurethane foams are typically produced from polyols with hydroxyl
numbers ranging from 300-500 mg KOH/g while biomass typically has hydroxyl
numbers around 1500 mg KOH/g. Therefore, the amount of biomass used have to be
52
PFs have attracted great attention due to its perfect fire resistant, low fire toxicity, high
dimensional stability, and low thermal conductivity comparing the other foam types.
There are a few studies regarding the preparation PF from liquefied lignocellulose based
resol resin. Lee et al (2002) liquefied the wood into phenol in the presence of sulfuric
acid catalyst at a moderate temperature of 150 °C under constant stirring and reflux. The
liquefied wood was used to prepare resol resin by the reaction with formaldehyde under
alkaline conditions. The obtained liquefied wood-based resol resin was applied for the
preparation of the phenolic foam. The resin mixed together with the poly (ethylene
ether) of sorbitan monopalmitate as a surfactant, hydrochloric acid as a catalyst, and
diisopropyl ether as a blowing agent. The obtained foams showed satisfactory densities
and compressive properties, comparable to those of foams obtained from conventional
resol resin. The resol-type resin was also prepared from the liquefied products of walnut
shell into phenol by Huang et al (2011). They successfully applied the biomass-based
resol resin to produce phenolic foam with diisopropyl ether as the blowing agent,
Tween 80 as the surfactant and hydrochloric acid as the catalyst, respectively. The
obtained foams showed satisfactory mechanical properties and a uniform fine cellular
structure.
REFERENCES
Alma, M.H., Basturk M.A. (2003). New polyurethane-type rigid foams from liquified
wood powders. Journal of Materials Science Letters, 22, 1225 – 1228.
Gao, L. L., Liu, Y. H., Lei, H., Peng, H., Ruan, R. (2010). Preparation of semirigid
polyurethane foam with liquefied bamboo residues. Journal of Applied Polymer
Science, 116(3), 1694-1699.
Huang, Y., Zheng, Z., Feng, H. Pan, H. (2011). Phenolic foam from liquefied products
of walnut shell in phenol, Advanced Materials Research 236-238, 241-246.
Lee, S.-H., Teramoto, Y., Shiraishi, N. (2002). Resol-type phenolic resin from liquefied
phenolated wood and its application to phenolic foam. Journal of Applied Polymer
Science, 84, 468–472.
Pan, H., Zheng, Z., Hse, C.Y. (2012). Microwave-assisted liquefaction of wood with
polyhydric alcohols and its application in preparation of polyurethane (PU) foams.
European Journal of Wood and Wood Products, 70(4), 461-470.
Pilato, L. (2010). Phenolic Resins: A Century of Progress, Springer-Verlag Berlin
Heidelberg, USA, 534 p.
Yaoguang, Y., Yoshioka, M., Shiraishi, N. (1996). Water absorbing polyurethane foams
from liquefied starch, Journal of Applied Polymer Science, 60, 1939-1949.
Zhang, J.P., Du, M. H., Hu, L.S. (2012). Bamboo liquefaction with polyhydric alcohols
and its application in flexible polyurethane foam. Advanced Materials Research 524,
2113-2117.
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Analytical methods for the investigation of the water - biodegradable
films interaction
Interaction of water with CNC films
Bianca-Ioana Dogaru, Maria-Cristina Popescu, Carmen-Mihaela
Popescu
Petru Poni Institute of Macromolcular Chemistry of the Romanian Academy, Iasi, Romania
[email protected], [email protected], [email protected]
Imola Herceg, Emília Csiszár
Budapest University of Technology and Economics, Department of Physical Chemistry and
Materials Science, H-1521 Budapest, Hungary. [email protected],
[email protected]
Keywords: surface energy, water sorption, contact angle, amino-aldehyde resin
ABSTRACT
Keywords: water sorption, NIR spectroscopy, contact angle measurements
ABSTRACT
Water plays an essential role in all living bodies and the hydrogen bonding between
water molecules is induced by the electrostatic interaction between the negative oxygen
atom and positive hydrogen atom of a neighboring water molecule. In aqueous polymer
systems, interaction between water and a polymer chain is highly important to
determine the physical properties of the systems in wide concentration regions. On the
other side, water sorbed into polymeric materials, in solid state, from the air or the
aqueous medium often causes a significant change in mechanical properties of the
polymers and suggests the domain of applicability.
In this context, the understanding of the effect of absorbed water molecules (moisture)
on the molecular interactions and relaxation dynamics in polymer networks is an
interesting and fundamentally important problem.
The sorption of water molecules induces usually swelling behavior is a polymeric
network. The later one depends on the polymer nature, composition of polymeric
system, molecular mass, degree of crosslinking and the compatibility between the
polymer and the solvent. Two types of water, hydrated water and bulk water, are
distinguishable in the vicinity of a polymer/water interface. Hydrated water is sorbed
inside of the polymer matrix where molecular interactions are involved; whereas bulk
water exists outside of the polymer matrix as liquid water.
In the present study, the interaction between water molecules and PVA/S/CNC film has
been explored by water vapor sorption tests, NIR spectroscopy and contact angle
measurements. The water vapor sorption was evaluated by static method using the
saturated salts solutions with different values of the RH. It has been observed that the
amount of water adsorbed decrease with the increasing of the S and CNC content. At
the same time, information on the amount and interactions involved were obtained from
the bands assigned to O-H stretching from water molecules from the NIR spectra.
Over the past twenty years, there has been intense and continuing interest in the
development of new and high value-added cellulose based materials to increase the use
of cellulose in consumer and industrial products. Currently, the fastest growing research
activity is concentrating on nanocelluloses, the novel forms of cellulose, because they
are renewable, environmentally sound and biodegradable. Of the three main types of
nanocelluloses (i.e. microfibrillated, nanocrystalline and bacterial nanocellulose), the
cellulose nanocrystals (CNC) are prepared from different cellulose containing sources,
such as lignocellulose based biomass, wood, cellulosic fibres, etc. by removal of the
amorphous phase with acid hydrolysis usually followed by an ultrasonic treatment in
order to disintegrate the aggregates of liberated crystalline cellulose particles.
Nanocelluloses can be used in several areas. Recent results proved that nanocellulose
based films can be good candidates for packaging materials in different fields (Oksman
et al., 2016; Kontturi et al. 2006)
In this research cellulose nanocrystals (CNC) were prepared from bleached cotton fibres
with sulphuric acid hydrolysis (Csiszar et al. 2016), and from the CNC suspension
nanocomposite films were prepared wherein the cellulose nanowhiskers were
crosslinked with an amino-aldehyde resin. The water-film interaction and the surface
energy of the films were systematically evaluated by measuring the contact angle and
the water sorption capacity as a function of the resin content (from 0 % to 30 %).
Results revealed that the increasing concentration of resin was associated with lower
moisture uptake by the films. At higher resin concentration the disintegration rate of
films by water decreased significantly.
REFERENCES
Oksman, K., Aitomäki, Y., Mathew, A.P., Siqueira, G., Zhou, Q., Butylina, S.,
Tanpichai, S., Zhou, X., Hooshmand, S. (2016) Review of the recent developments in
cellulose nanocomposite processing, Composites: Part A, 83, 2-18.
Kontturi, E., Tammelin, T., Österberg, M. (2006) Cellulose – model films and the
fundamental approach. Chem. Soc. Rev., 35, 1287-1304.
Csiszar, E., Kalic, P., Kobol, A. and Ferreira, E.P. (2016). The effect of low frequency
ultrasound on the production and properties of nanocrystalline cellulose suspensions
and films. Ultrasonics & Sonochemistry, 31, 473-480.
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
Poster presentations II
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II
Nanocomposite films based on cellulose nanocrystals and
titanium dioxide nanoparticles
Bio-inspired nanocomposite films and foams from resilin-CBD
bound to cellulose nanocrystals
David Leibler, Oded Shoseyov
T. Ben Shalom1, A. Rivkin1, T. Abitbol1, Yuval Nevo1, 2, S. Lapidot2
and O. Shoseyov1
The Hebrew University of Jerusalem, The Robert H. Smith Faculty of Agriculture, Food and
Environment, P.O.B 12 Rehovot, Israel. [email protected]
Keywords: cellulose nanocrystals, TiO2 nanoparticles, UV-blocking
1
The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew University of
Jerusalem, Rehovot 76100, Israel. [email protected]
2
Melodea Ltd. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew
Universit y of Jerusalem, Rehovot 76100, Israel
ABSTRACT
Preliminary studies were conducted to assess the properties and stability of aqueous
mixtures of cellulose nanocrystals (CNCs) and TiO2 nanoparticles (NPs) using
dynamic light scattering (DLS) and zeta-potential measurements. Conditions (e.g.,
pH, concentration) were found where the mixtures were colloidally stable, essentially
at pH values where both types of NPs had a negative surface charge. The stable NP
mixtures were cast into films that possessed mechanical properties similar to neat
CNC films but optical properties (i.e., UV-blocking) related to the TiO2 NPs. These
films are of interest for UV-blocking cellulosic coatings that may be useful for
various applications, such as in packaging.
Keywords: Bio composite, cellulose nanocrystals, resilin, self-assembly
ABSTRACT
The arthropod cuticle and the plant cell wall are examples of the remarkable composite
materials that support survival in nature. Inspired by the elasticity of insect's cuticle and
the strength of plants cell wall, E. coli was genetically engineered in order to produce
recombinant resilin fused to a cellulose binding domain (res-CBD). The rubbery
characteristics of resilin-like proteins and the binding of the res-CBD to cellulose
nanocrystals (CNCs) has been previously explored by our group (Qin el al. 2011,
Rivkin et al. 2015).
The isolation and purification of cellulose nanocrystals involves a simpler, bottomdown approach, where CNCs are most commonly extracted by sulfuric acid hydrolysis
of native cellulose. CNCs from sulfuric acid hydrolysis form stable suspensions in water
due to repulsive interactions from charged groups grafted on during hydrolysis and
exhibit interesting self-assembly, optical and mechanical properties that make them
suited for a wide range of applications.
In terms of mechanical properties, resilin and CNCs are very different. The structure of
resilin, essentially an amorphous, hydrogel polymer, held together via di- and trityrosine crosslinks, imparts near perfect elasticity. In contrast to the flexibility and
relative softness of the resin, CNCs are highly crystalline, hydrogen bonded and
structured that imparts strength and stiffness that comparable to steel and Kevlar®.
This work explores the properties of bionanocomposite foams and films prepared by
binding res-CBD to CNCs.
REFERENCES
Qin G, Rivkin A, Lapidot S, Hu X, Preis I, Arinus SB, Dgany O, Shoseyov O and
Kaplan DL (2011). Recombinant exon-encoded resilins for elastomeric biomaterials.
Biomaterials. 32, 9231-43.
Rivkin A, Abitbol T, Nevo Y, Verker R, Lapidot S, Komarov A, Veldhuis S.C,
Zilberman G, Reches M, Cranston E.D and Shoseyov O. (2015). Bionanocomposite
films from Resilin-CBD bound to Cellulose Nanocrystals. Industrial Biotechnology. 11,
44-58.
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COST ACTION FP1205 BUDAPEST 22-23 September 2016
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COST (European Cooperation in Science and Technology) is a pan-European
intergovernmental framework. Its mission is to enable break-through scientific
and technological developments leading to new concepts and products and
thereby contribute to strengthening Europe’s research and innovation capacities.
It allows researchers, engineers and scholars to jointly develop their own ideas
and take new initiatives across all fields of science and technology, while
promoting multi- and interdisciplinary approaches. COST aims at fostering a
better integration of less research intensive countries to the knowledge hubs
of the European Research Area. The COST Association, an International notfor-profit Association under Belgian Law, integrates all management, governing
and administrative functions necessary for the operation of the framework. The
COST Association has currently 36 Member Countries.
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