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University of Coimbra, DEQ & DCV
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University of Coimbra, DEQ & DCV
COST Action FP1105
“Understanding wood cell wall structure, biopolymer interaction and composition:
implications for current products and
new material innovation”
Department of Chemical Engineering
and
Department of Life Sciences
University of Coimbra
Portugal
May 8-9, 2014
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University of Coimbra, DEQ & DCV
The organizers acknowledge the support of the
following institutions:
Banco Bilbao Viscaya Argentaria (BBVA)
Caixa Geral de Depósitos (CGD)
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University of Coimbra, DEQ & DCV
Contents
Cost 5
Organisers 6
Agenda 7
Workshop’s rooms allocation 13
Keynote presentations 14
Short presentations 26
Posters 38
Useful information 74
List of participants 82
Notes 85
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University of Coimbra, DEQ & DCV
COST
COST is an intergovernmental framework for European Cooperation in Science and
Technology, allowing the coordination of nationally-funded research on a European
level. COST contributes to reducing the fragmentation in European research
investments and opening the European Research Area to cooperation worldwide. The
goal of COST is to ensure that Europe holds a strong position in the field of scientific
and technical research for peaceful purposes, by increasing European cooperation and
interaction in this field. This research initiative makes it possible for the various
national facilities, institutes, universities and private industry to work jointly on a wide
range of Research and Development (R&D) activities.
COST Action FP1105
The primary objective of the proposed Action is to build knowledge and understanding
of fundamental physical (self assembly) processes and biological systems (e.g. genetic
control) that drive natural structures and biopolymer composition within the plant/wood
cell wall and to use new knowledge of self assembly processes to support the
development of new biopolymer based materials.
The Action also aims to quantify the impact of new knowledge on our understanding of
the mechanical properties of the cell wall and how processes such as pulping, bleaching
recycling, cell wall disintegration methods and ongoing tree improvement and
biotechnology programmes impact both positively and negatively on structure and
composition of the cell wall. The intent is to explore how this knowledge can be used to
support ongoing improvement in these areas of activity. An overarching goal is to
develop multidisciplinary competence and capability to support these objectives and to
work closely with commercial organisations to promote effective dissemination of
knowledge and the development of a more economically sustainable Forest Based
Sector.
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University of Coimbra, DEQ & DCV
Organisers
Jorge M. Canhoto (Department of Life Sciences)
Paulo J. Ferreira (Department of Chemical Engineering)
Ana F. Lourenço (Department of Chemical Engineering)
Sandra Correia (Department of Life Sciences)
João Martins (Department of Life Sciences)
Sara Rodrigues (Department of Life Sciences)
PRODEQ – Associação para o Desenvolvimento da Engenharia
Química
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University of Coimbra, DEQ & DCV
1. Agenda
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University of Coimbra, DEQ & DCV
COST Action FP1105: Agenda for Coimbra Meeting, May 8-9 2014
8th
of May 2014
08:30 - 09:00 Registration (attendance list signature).
09:00 - 09:30 Welcome and Introduction to the workshop by the Action chair,
Philip Turner
09:30 - 10:00 Presentation from the host:
Prof. Jorge Manuel Rocha (head of the Department of Chemical
Engineering)
Prof. Graça Rasteiro (head of the Chemical Process Engineering and
Forest Products Research Centre)
Prof. Jorge Canhoto (Organizing Committee)
Prof. Paulo Ferreira (Organizing Committee)
10:00 - 12:00 2 Presentations (20mins + 10mins)
Session chair: Tomas Larsson
10:00 - 10:30 Lindström, Tom: The emergence of commercial nanocellulose
applications - an overview of the state of the art
10:30 - 11:00 Coffee Break
11:00 - 11:30 Larsson, Tomas: The latest developments on cellulose structure
& reactivity
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University of Coimbra, DEQ & DCV
11:30 - 12:15 Poster presentations (7)
Session chair: Philip Turner
Costa, Guy: Microwave ionic liquid activation coupled with mAb
macroarray detection as a rapid and easy tool kit for polysaccharides
analysis.
Fernando, Dinesh: Morphological ultrastructural characteristics of
fines fraction produced during Hc and Lc refining of Tmp for
fundamental understanding of property development.
Angelini, Stefania: Effect of chemical-physical treatments on a
lignocellulosic biomass properties and solubility.
Latifi, Kourosh: Sample preparation for fibre-fibre wet friction
measurement
Urruzola, Iñaki: Reinforcement paper with nanofibers using eucalyptus
pulp as raw material
Valchev, Ivo: Influence of the lignocellulosic structure on the kinetic
model of enzymatic hydrolysis
Galvis, Leonardo: Structural and chemistry analysis of barley
endosperm by polarized Raman spectroscopy (PRS)
12:15 - 14:00 Poster session & Buffet lunch
14:00 - 14:30 Poster presentations (6)
Session chair: Jorge Canhoto
Aguié-Béghin, Veronique: Designed lignocellulose-based films for
tunable physico-chemical and spectral properties
Gawdzik, Barbara: Lignin modified porous Bpa.Da-St polymers
characterised by thermal analysis
Gordobil, Oihana: Xylan-cellulose films: improvement of
hydrophobicity, thermal and mechanical properties
Heinemann, Sabine: Microfibril angles of softwood and hardwood pulp
fibres
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University of Coimbra, DEQ & DCV
Kuncova-Kallio, Johana: MP-SPR: A new optical technique for
characterization of cellulose structure and kinetic interactions
Niinivaara, Elina: Humidity response of thin films consisting of
alternating layers of amorphous and crystalline cellulose
14:30 - 16:00 3 Presentations (20mins + 10mins)
Session chair: Gary Chinga
14:30 - 15:00 Crestini, Claudia: Tannins characterization By 31
p-Nmr
15:00 - 15:30 Mikczinski, Manuel: Revisiting the transverse compression
modulus
15:30 - 16:00 Vilaseca, Fabiola: Use of Nfc in papermaking applications
Mendez, Jose Alberto: Lepamap Group. Research lines
16:00 - 16:30 Poster presentations (6)
Session chair: Pasi Kallio
Peyre, Jessie: Tuning the assembly of cellulose nanocrystals in 2D
networks by adjusting the chemical conditions in spin coating
Podkoscielna, Beata: Synthesis and copolymerization of new acrylate
derivatives of lignin
Robles, Eduardo: Nanopaper from almond shell
Salminen, Reeta: Cellulose block copolymers
Sokolov, Alexander: Pulsed corona discharge oxidation in lignin
modification
Trifol, Jon: Synergetic behaviour of clay and cellulose nanofibers on
barrier properties of nanocomposite
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University of Coimbra, DEQ & DCV
16:30 - 17:30 Poster session & drinks
20:00 Dinner
9th
of May 2014
08:30 - 09:00 Registration and Reimbursement Forms collection.
09:00 - 12:30 3 Presentations (20mins + 10mins) and
6 STSM presentations (10mins + 5mins)
Session chair: Claudia Crestini and Geoffrey Daniel
09:00 - 09:30 DelliColli, H. T.: Lignin in the future, an item of commerce
09:30-10:00 Argyropoulos, Dimitris: Our industry’s need to refine lignin prior
to use in a way similar to crude
10:00 - 10:15 Gangula, Sheetal: Quantitative studies of oligomeric mixtures by
MALDI-ToF-MS (STSM)
10:15 - 10:30 Penttila, Paavo: Visualization of elastic properties in biopolymer
composites using ultrasonic force microscopy (STSM)
10:30 - 11:00 Coffee break
11:00 - 11:15 Hidalgo, Jokin: Microscopic characterization of organic-
inorganic hybrid nanosystems (STSM)
11:15 - 11:30 Svard, Antonia: Effect of raw material and pulping conditions on
dissolved kraft lignin; characterization of kraft lignins from pine,
spruce and eucalyptus by elemental analysis (CHNS/O) and
analytical pyrolysis (Py-GC/MS) (STSM)
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11:30 - 11:45 Leitner, Johannes: Treatment of pulp in a kneader and disperger
(STSM)
11:45 - 12:15 Marques, Cristina: RAIZ R&D contribution to eucalypt forest
productivity in Portugal
12:15 - 13:30 Lunch and poster session
13:30 - 15:00 Working Groups meetings
15:00 - 16:00 WG feedback & Open discussion
16:00 – 16:30 Coffee break
16:30 - 17:00 Management Committee Meeting
17:00 - 18:00 Core group meeting
18:00 End of the workshop
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University of Coimbra, DEQ & DCV
Workshop’s rooms allocation
Sessions: Noble Auditorium (-2 floor)
WG1 meeting: Noble Auditorium (-2 floor)
WG2 meeting: Room C07 (-2 floor)
WG3 meeting: Meeting Room (-1 floor)
Management Committee meeting: Noble Auditorium (-2 floor)
Core Group auditorium: Noble Auditorium (-2 floor)
Lunches: Stone House (yellow house near the Department of Chemical Engineering)
Posters: Hall (floor -2)
Coffee Breaks: Hall (floor -2)
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2. Keynote presentations
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Non-cell autonomous post-mortem lignification of xylem vessels
Edouard Pesquet, Umeå Plant Science Centre, Sweden.
Lignification and programmed cell death (PCD) are of fundamental importance to the
production of functional tracheary elements (TEs) – a cellular corpse which requires
PCD to hollow out its content and lignification to reinforce its wall to transport sap.
Live cell imaging of TE formation showed that lignification occurred after TE PCD
(Pesquet et al., 2010). The interplay between PCD and lignification during TE
formation was studied at the cellular level using in vitro xylogenic cultures, at the
genomic level using differential subtractive libraries and at the whole plant level by
analyzing the cell wall biochemistry of 51 Arabidopsis KO mutants in newly identified
genes differentially responding to TE PCD inhibition. Pharmacological modulation of
TE lignin monomer biosynthesis resulted in dead unlignified TEs, which could partially
lignify post-mortem when supplied externally with lignin monomers. Pharmacological
modulation of TE PCD in the differentiating TEs blocked both cell death and
lignification without affecting xylan/cellulose secondary wall deposition. Differential
libraries constructed from TE cell cultures inhibited or not to perform PCD allowed to
identify 693 differentially expressed genes involved in PCD-triggered lignification.
Among these genes were identified known cell wall biosynthesis, lignin monomer
biosynthesis and PCD related genes. Interestingly, cinnamoyl-CoA reductase (CCR)
and cinnamyl alcohol deshydrogenase (CAD), two lignin monomer synthesis genes,
were expressed beyond normal TE lifespan. In situ localization using IS-RT-PCR of
CAD and CCR revealed that both genes were expressed in cells analogous to xylem
parenchyma. Cell wall composition analysis of 51 Arabidopsis mutants in genes
differentially responding to TE PCD inhibition were characterized by reverse genetic
approaches and exhibited changes in lignin composition in whole plants although gene
expressions were restricted to xylem parenchyma. Altogether, our results suggest that
lignin is mostly made through a post-mortem and cooperative process in xylem vessels
(Pesquet et al., 2013).
References
Pesquet E., Korolev A.V., Calder G. and Lloyd C.W. (2010) The microtubule-
associated protein AtMAP70-5 regulates secondary wall patterning in Arabidopsis
wood cells. Current Biology, 20, 744-749.
Pesquet E., Zhang B., Gorzsás A., Puhakainen T., Serk H., Escamez S., Barbier O.,
Gerber L., Courtois-Moreau C., Alatalo E., Paulin L., Kangasjärvi J., Sundberg B.,
Goffner D. and Tuominen H. (2013) Non-cell autonomous post-mortem
lignification of tracheary elements in Zinnia elegans. Plant Cell, 25, 1314-28.
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The emergence of commercial nanocellulose applications - an overview
of the state of the art
Tom Lindström, Drottning Kristinas väg 61, 114 86 Stockholm, Sweden.
There has been extensive research and development activities in the field of
nanofibrillated cellulose (NFC) materials during recent years, although microfibrillated
cellulose (now NFC) was developed already during the late 70s at ITT-Rayonier in
USA.
A major impediment for the large-scale use of NFC has been the high-energy use
(excess of 25000 kWh/ton NFC) for its energy use. This problem has now been
alleviated by a series of different pre-treatment procedures of the fibres prior to the
subsequent mechanical cell wall delamination.
The focus in practical papermaking applications of NFC is in the reinforcement of
paper/board materials (dry strength wet-end additive) and in barrier coating
applications.
The driving forces in these applications are resource and energy efficiency in
papermaking and the vision of substituting fossil-based films with nanocellulose
barriers. Nanocellulose has excellent oil, fat and oxygen barrier properties in the dry
state, but the oxygen barrier properties are deteriorated at high relative humidities and
approaches to alleviate the moisture sensitivity will be discussed.
Today, there are many companies in the process of commercializing NFC and several
companies have pilot plants/pre-commercial operations and are planning for up scaling.
A pilot plant for the nominal production of 100 kg/day (dry based NFC) was also taken
into operation at Innventia AB 2010.
The current contribution will highlight critical issues in the production of NFC and
discuss various applications and hurdles to overcome in order to make NFC production
for various end-use applications viable.
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Designing ‘reactive’ pulp fibres
Tomas Larsson, Innventia AB
The presentation describes results relating to reactive pulp fibres. The aim of the work
has been to develop pulp qualities for purposes other than traditional papermaking; the
concept of reactivity becomes quite diverse when pulps are to be adapted for enzymatic
hydrolysis or good solubility. The adaption of pulps is made within the boundaries of
existing processing equipment by altering processing conditions in order to reach the
desired pulp properties. The typical, never-dried, pulp manufactured have a high
cellulose content, a high specific surface area, large fibre wall pores and with a
controlled molecular mass distribution.
Designing cellulose rich fibres for different kinds of reactivity puts a strong focus on the
supramolecular structure characterizing isolated cellulose I and also connects with the
fibre wall morphology.
Some examples will be shown where pulp has been successfully designed for ease of
enzymatic hydrolysis and some comments will be made with respect to the degree of
cellulose crystallinity.
A second area of reactivity is related to the dissolution of cellulose for textile fibre
manufacture. In this context the reactivity relates to the ease of dissolution and some
recent molecular dynamics simulation results relating to the properties and behaviour of
-(1,4)-D-glucan will be addressed
Some additional questions will be raised regarding the degree of crystallinity of isolated
cellulose I and its relation to ‘reactivity’.
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Tannins characterization by 31
P-NMR
C. Crestini, Department of Chemical Sciences and Technologies, University of Rome ‘Tor
Vergata’, Via della Ricerca Scientifica, 00133 Rome, Italy.
Tannins are naturally occurring plant polyphenols. Their main characteristic is that they
bind proteins, basic compounds, pigments, large molecular weight compounds, and
metallic ions and display antioxidant activities. The extensive presence of tannins in a
variety of foods, possessing many variable structures, creates formidable analytical
challenges. These challenges are applicable to both isolated tannins and tannins in complex
matrices. The biological activities displayed by tannins are due to the variable amounts and
regiochemical details of their phenolic OH groups, which actually regulate their protein-
binding capacities and their antioxidant activities. As such, the specific characterization of
the regiochemical patterns of the phenolic groups in tannins and their quantification
represent an invaluable tool for the study of their characteristics and the evaluation of
quality and activity of a widespread array of foods, feeds, and nutraceutical products.
However, the characterization and analysis of tannins are difficult due to their complex
structure and low solubility in organic solvents. They often occur in complex mixtures
difficult to standardize and quantify. The most widely used methods of analysis are based
on the general determination of the phenolic group content, on the overall condensed or
hydrolyzable tannin content (using specific functional group assays), and on protein
precipitable methods. Because different phenolic groups give different responses to such
methods of analysis, the “tannin level” or “phenolic level” of a sample cannot
be adequately expressed as a single value. Another major limitation common to all
methods of analysis lies in the difficulty of preparing appropriate standards. Varying
responses observed for different tannins prevent the use of a single commercially available
compound as a convenient standard, because the relative responses of the standard and the
sample in the assay are not known. Structural differences in tannins and their biological
activities can be better evaluated by taking into consideration the aromatic ring substitution
patterns that present phenolic, catecholic, ortho-substituted, and ortho-disubstituted
phenolic groups, because these moieties are responsible for the metal binding and
antioxidant properties of tannins.
An unprecedented analytical method that allows simultaneous structural and quantitative
characterization of all functional groups present in tannins is reported. In situ labeling of
all labile H groups (aliphatic and phenolic hydroxyls and carboxylic acids) with a
phosphorus-containing reagent (Cl-TMDP) followed by quantitative 31P NMR acquisition
constitutes a novel fast and reliable analytical tool for the analysis of tannins and
proanthocyanidins with significant implications for the fields of food and feed analyses,
tannery, and the development of natural polyphenolics containing products. We developed
a new analytical method for the structural characterization of tannins based on the 31
P-
NMR technique. In particular, samples of tannins isolated from different wood species and
purchased from enological companies were phosphitylated and then subjected to the 31P
NMR analysis. The assignment of the different OH signals was carried out on the basis of
the comparison with the chemical shift of selected models, as reported in literature, and by
the 31
P-NMR analysis of tannins model compounds.
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Revisiting the transverse compression modulus Manuel Mikczinski, OFFIS - Institute For Information Technology, Escheeweg 2, D-
26121 Oldenburg, Germany.
Micro- and nanorobotic systems are slowly becoming an integral part of single fibre
investigations. In the last few years different robotic systems and different handling and
characterisation strategies were presented to manipulate single fibres. One of these is
the transverse compression of individual fibres (Mikczinski, et al., 2011).
The transverse compression was already investigated before with more basic equipment.
Individual fibres were pressed between glass plates (Nyrén, 1971) or compressed in a
hammer-anvil arrangement (Wild, Omholt, Steinke, & Schuetze, 2005). Microrobotic
compression was only recently reported (Mikczinski, Nguyen, & Fatikow, 2013). From
these measurements it is expected to gain additional knowledge about the composition
and behaviour of single fibres. Numerical simulations (Shiari & Wild, 2004) and
analytical descriptions are used to improve and verify the understanding.
Earlier experiments (Wild, Omholt, Steinke, & Schuetze, 2005) showed only two
distinct parts in the fibre thickness to compression load curve: (i) the collapsing part and
(ii) the compression part. Both parts can be seen in the results as smoothly transforming
from one into the other. A simple compression modulus was used to describe this
behaviour (Wild, Omholt, Steinke, & Schuetze, 2005):
with ET as the tangent modulus, (dF/dt) as the slope of the force-distance curve in the
region with collapsed lumen, and the fibre dimensions t (thickness), L (compressed
length), and w (width). The inverted comma denotes that these are fitted for a reference
stress level, which was determined during testing.
However, it was shown with a more sensitive sensor and a nanorobotic setup, that there
are more regimes that need to be considered in the compression cycle (Mikczinski,
Nguyen, & Fatikow, 2013). Figure 1 shows the load-displacement curve of a single
fibre during loading (left curve) and unloading (right curve). The schematic drawings
show different possible states during loading. It is therefore proposed to establish a new
description of the different compression states.
At least two regimes can be distinguished and represented by a corresponding modulus.
First, the collapsing of the fibre (EColl) and secondly, the fibre wall compression (EFW).
With a combination of different modules the different effects and behaviours can be
described, which allows also introducing a modulus derived from composite
technology.
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References
Mikczinski, M., Bartenwerfer, M., Saketi, P., Heinemann, S., Passas, R., Kallio, P., &
Fatikow, S. (2011). Towards Automated Manipulation and Characterisation of
Paper-making Fibres and its Components. In P. Ander, W. Bauer, S. Heinemann,
P. Kallio, R. Passas, & A. Treimanis, Fine Structure of Papermaking Fibres (pp.
163-178). Uppsala, Sweden: Swedish University of Agricultural Sciences.
Mikczinski, M., Nguyen, H. X., & Fatikow, S. (2013). Assessing Transverse Fibre
Properties: Compression and Artificial Hornification by Periodic Compression. In
S. J. I'Anson, Advances in Pulp and Paper Research (Bd. 2, S. 803-820). Bury,
Lancashire, UK: The Pulp and Paper Fundamental Research Society, FRC.
Nyrén, J. (1971). The Transverse Compressibility of Pulp Fibres. Pulp and Paper
Magazine of Canada, 72(10), S. 81-83.
Shiari, B., & Wild, P. M. (2004). Finite Element Analysis of Individual Wood-Pulp
Fibers Subjected to Transverse Compression. Wood and Fiber Science, 36(2), S.
135-142.
Wild, P. M., Omholt, I., Steinke, D., & Schuetze, A. (2005). Experimental Characterization
of the Behaviour of Wet Single Wood-Pulp Fibres under Transverse Compression.
Journal of Pulp and Paper Science, 31(3), S. 116-120.
Figure 1. Load-displacement curve of an individual fibre in transverse compression.
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Use of NFC in papermaking applications
González, I.; Alcalà, M.; Pèlach, M.A.; Vilaseca, F.; Mutjé, P. LEPAMAP Group,
Dept. of Chemical Engineering, University of Girona, C/ M. Aurèlia Capmany, 61, 17071
Girona (Spain), [email protected]
During the coming years, paper industry will need to implement different strategies in
order to prevent the use of large amounts of virgin cellulosic fiber, for the sake of
saving forest resources. According to recent literature, the forthcoming strategies will be
mainly to convert recycling a central part of paper activities, the diminishing of basis
weight of paper-based products, and the major use of fillers instead of fiber content in
the paper formulation.
Among these approaches, it is expected that the use of nanofibrillated cellulose (NFC)
will become a real fact in paper industry. NFC can be applied in bulk during paper
production or at paper surface at the last steps of papermaking. The addition of NFC as
component of paper formulation, intended to enlarge paper strength, has to be done at
moderate levels otherwise the drainage of the suspension is hindered, and so the
runnability during paper production. In order to overcome this problem, some
alternatives can be employed, such as the use of biobeating followed by the addition of
minor amounts of NFC in the formulation. This procedure has given out reasonable
results when applied to bleached hardwood and softwood pulps, as well as to secondary
fibers or to fibers from agricultural residues. Another possibility is related to the use of
NFC on paper surface as dry strengthening agent. For this purpose, porous paper
structures seem to favor the effect of NFC.
In this work, several alternatives are proposed as substitutes of classic mechanical
beating. Therefore, increasing amounts of NFC has been applied to non-beating fiber
substrates. The paper strength of the paper was improved, and the drainability of the
suspension was controlled following different options. It was demonstrated that
mechanical beating can be partly replaced, and that this prevents the energy
consumption during papermaking as well as the damaging of cellulose fibers, which is a
very important aspect especially when they are submitted to subsequent recycling loops.
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LEPAMAP group. Research lines
José Alberto Méndez, Fabiola Vilaseca, M. Àngels Pèlach, Josep Puig, Pere Mutjé LEPAMAP group. University of Girona. EPS, building PI, C/. Maria Aurèlia Capmany 61,
17071, Girona, Spain. [email protected]
The LEPAMAP group of the University of Girona is a multidisciplinary research group
based on chemists, biologists and engineers, focusing their research work in materials
science based on lignocellulose. This research is performed in 10 laboratories or units as
showed in the following table.
L-1, Laboratory of chemistry and technology of fibrous materials
L-2, Laboratory of nanopaper
L-3, Laboratory of secondary fibres
L-4, Laboratory of paper biotechnology and nanotechnology
L-5, Laboratory of all lignocellulosic composites
L-6, Laboratory of composite materials
L-7, Laboratory of chemical and biochemical technology
L-8, Laboratory of assays
L-9, Laboratory of life cycle analysis
L-10, Laboratory of food contact
Our research lines include from the acquisition and characterisation of the raw material
(hard/softwood, annual plant, agroforest residues, recycled paper, mechanical pulp)
until the application of the fibres (micro and nano scale), passing through the processing
of NFC and biobiting and the incorporation of the fibres inside the substrate (mainly
thermoplastic polymer matrices and paper).
- (L-1) (R.R*.: N. Pellicer/ P. Mutjé) The raw materials, mainly agroforestal residues,
are processed by different ways in order to obtain lignocellulosic pulps with high yield
(80% or higher) using different chemical approaches. The pulps are characterised to
determine the chemical properties and the properties of the derived papers. This unit
also provides fibres to units L-4, L-5, L-6 and L-7.
- (L-2) (R.R. F. Vilaseca/M.A. Pèlach) Fabrication of nanopaper and hybrids.
Nanopaper is considered a paper with a NFC content higher than 50 %wt. Hybrids are
obtained by incorporation of virgin cellulose fibres, refined or non refined, depending
on the application. L-2 also produces modified nanopapers with special properties:
electrical, magnetical, antimicrobial and others, by incorporation of specific
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University of Coimbra, DEQ & DCV
components: nanotubs, metallic particles, nanocarbonates and peptides. The material is
provided by L-4 and L-7.
- (L-3) (R.R.: M.A. Pèlach) Production of lignocellulose fibres from recycled paper,
friendlier with the environment. This research is justified by the increasing percentage
of recycled fibres in new paper products (more than 50% wt).
- (L-4) (R.R.: P. Mutjé) Fabrication of papers by means of alternative techniques: Bulk
modification (NFC incorporation and biobeating), increase of their mineral content and
surface treatment (NFC and nanofillers, dry-strength agents).
- (L-5) (R.R.: G. Arbat/P. Mutjé) Development of all lignocellulosic materials by using
just own lignin, coming from agroforestal residues (mainly cereal straws), as
bioadhesive. To improve of mechanical properties, the materials are modified with kraft
lignin and NFC produced in L-7. The production is based on a wet procedure and
thermoconforming.
- (L-6) (R.R.: X. Espinach/F. Julián) Development of composite materials
reinforced/loaded with lignocellulosic fibres (strands, wood fibres, agroforestal
residues, wood dust and mineral reinforcements). This reinforcement is incorporated
into thermoplastic biodegradable and non biodegradable polymer matrices. The
processing is based on a kinetic mixing process and transformation by injection-
moulding or extrusion. This unit also includes the characterisation of the obtained
materials as well as its valorisation in a final piece by "rapid prototyping".
- (L-7) (R.R.: F. Vilaseca/J.A. Méndez) (L-7.1) Production and characterisation of NFC
coming from wood fibres, annual plants and agroforestal residues. NFC produced in this
unit acts as raw material in L-2, L-4 and L-5. (L-7.2) Production of bacterial cellulose.
Coming soon: Chemical modification of NFC for specific applications and valorisation
as biomaterials for biomedical applications.
This unit also acts a laboratory of microscale for nanopaper production prior to L-2 up-
scaling.
- (L-8) (R.R.: M. Alcalà/M.A. Pèlach) Laboratory of physical-chemical assays:
mechanical, optical, electrical and magnetical properties. Moreover characterisation of
specific properties: barrier and antibacterial properties, water uptake and thermal and
acoustic isolation.
- (L-9) (R.R.: M. Delgado-Aguilar/J. Pujol) Unit of life cycle analysis of the produced
materials, comparing it with that of those of existing materials in the market.
- (L-10) (R.R.: J. Puig) Laboratory of food contact focused in the characterisation of
paper products to be used in contact with aliments.
Resuming, LEPAMAP group is a fully integrated research group to tackle the
exploitation of the countless possibilities of use of cellulose, from a micro as well as
nano point of view.
*R.R.: Responsible researcher.
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Lignin in the future, an item of commerce
H.T. DelliColli Ph.D., Principal, R-Theta Consulting LLC, Charleston, South Carolina, USA.
Since its initial identification by Payen 176 years ago, approximately 2% of the 50
million metric tons of lignin produced annually, by the world’s pulp mills and
biorefineries, is sold as “items of commerce”. The remainder is either burned as fuel or
disposed of according to Federal, state and/or local environmental regulation. Why? In
only 66 years man’s science and technology has taken him from Kitty Hawk, North
Carolina to the moon. Is the commercialization of lignin any more difficult than “rocket
science?” Is it a question of need, a lack of problems requiring solutions, better and
cheaper alternative solutions to these problems? Perhaps these reasons and others have
placed barriers of misunderstanding, misinformation, and misdirection in the path
towards commercialization of high performance value added products and technology
based on lignin.
The early and successful application of lignosulfonates and their identification as waste
products from wood pulping led to the view that lignin was a low value material, more
suitable for use as a fuel than what it really is, a highly effective dispersant. The failure
of industry to treat the by-products of biomass deconstruction in a manner parallel to
that applied to petroleum further retarded lignin commercialization.; The relegation of
lignin development to an industry whose operational paradigms runs contrary to the
successful development of high value chemical products based on lignin shares the
blame as well. Some from the academic community must also accept the responsibility
for perpetuating the belief that lignin is or should be available for pennies per kilogram.
It has created serious misconceptions on the part of the industries potentially capable of
advancing the commercialization.
Failure, on the part of many, to recognize that the key operational aspect of lignin
chemistry “IS CHEMISTRY”, has created an immediate need; a revisitation of many of
the previously published and much discussed aspects of lignin with the respect and
understanding usually accorded a bona fide chemical substance and feedstock.
Additionally, failure to find a working congruency between lignin chemistry and
chemical engineering has resulted in many failures at the pilot and commercial plant
levels. Such failures continue to plague the development of commercially successful
lignin technology.
Perhaps, these problems can be overcome by shrinking or hopefully eliminating the
barriers to commercialization mentioned above. It is a good place to start and the
research community, academic and industrial, is the group to do it.
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RAIZ R&D contribution to eucalypt forest productivity in Portugal
Cristina Marques, RAIZ, gPS
Due to their wide adaptability and excellent wood properties, eucalypts have been
adopted for plantation forestry around the world, becoming a truly “global” tree.
Among over 700 species in the genus, Eucalyptus globulus is considered a benchmark
for pulp & paper production, due to its basic density, fiber morphology, lignin
content/quality and pulp yield. Portugal host around 30% of E. globulus planted forest
area, in the world.
This presentation describes RAIZ commitment to support the competiveness and
sustainability of the Portuguese Pulp & Paper Industry, through research, technology
transfer and training in Pulp & Paper and Forestry research. In the Forestry division we
are dedicated to developing genetic materials & silvicultural practices that promote
productivity and improve wood properties, at minimum cost and environmental impact.
RAIZ in funded by the PortucelSoporcel group, Europe’s largest producer of bleached
eucalyptus kraft pulp. It is also one of the largest European producers of uncoated
wood-free paper.
The PortucelSoporcel group manages around 90 thousand hectares of eucalypt
plantations and deals with above 400 thousand private forest producers. E globulus
plantations face a significant number of biotic, abiotic and social challenges. Besides the
mostly very small size of plantations, the country is very rich in diverse edaphoclimatic
conditions and biotic stress has increased in the last decade. RAIZ Forestry research is
developed in an integrated model, using knowledge in Genetics, Biotechnology, Plant
Propagation, Soils & Nutrition, Forestry Protection, Ecophysiology and Biometry, to
consolidate discoveries into applications in forest management & operation. We nurture
national and international scientific collaborations in key areas. Moreover, we are
attentive of Technology Transfer both within the company and also with private
producers and organizations. In order to illustrate the importance of adequate
silviculture and choice of genetic materials, we maintain a network of model plantations
throughout the country, available to visitors.
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3. Short presentations
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Quantitative mass spectrometry of oligomers by MALDI-ToF-MS
Sheetal Gangula and Petra Mischnick, Technische Universität Braunschweig | Institute of
Food Chemistry
Polysaccharide derivatives are submitted to partial de-polymerization to study the
substitution pattern in the polymer chain [1]. Complex oligomeric mixtures are obtained
from this de-polymerization. For quantitative analysis of the composition of these
mixtures mass spectrometry (MS) is the method of choice. But is hampered by the fact
that only qualitative analysis is possible for quantitative analysis under certain
conditions compounds with different substituents i.e. chemistry show different molar
responses[2]. Hence directly correlating the peak intensity in mass spectra to molar
composition of compounds in a sample is not possible. Peak intensity in MS is not only
dependent on concentration of the components but also on ionizing efficiency in
combination with instrumental parameters [2]. The goal of our project is to study and
quantify the factors that influence the ratio of the relative ion intensities in defined
oligomeric mixtures. We have synthesized heptakis [2,3,6-tri-O-methyl]-β- cyclodextrin
(CD-Me21), the corresponding deuteromethyl (CD(Me-d3)21), ethyl (CDEt21) and
methoxyethylated-β-cyclodextrin (CD- MeOEt21). After partial hydrolysis, oligomers
were isolated and mixtures with known relative molar ratio were prepared details shown
in scheme 1.
Scheme 1: Showing flow of sample preparation starting from alkylated cyclodextrins with
different substituents and preparing a defined complex mixture to study the behaviour in mass
spectrum.
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These defined mixtures were used to study the relative ion yield in the mass spectrum
under defined conditions. Our study revealed some interesting facts about quantification
with mass spectrometry which will be presented.
References
1. P. Mischnick, D. Momcilovis, Adv. Carbohydr. Chem. Biochem, 2010, 64, 117-210.
2. P. Mischnick, Adv. Polym. Sci, 2012, 248, 105-174.
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Visualization of elastic properties in biopolymer composites using
ultrasonic force microscopy
Paavo A. Penttilä
a, Suvi Alakalhunmaa
b, Kirsi S. Mikkonen
b, Kirsti Parikka
b,
Maija Tenkanenb, Rirva Serimaa
a, M. Teresa Cuberes
c
a Department of Physics, University of Helsinki, Helsinki, Finland
b Department of Food and Environmental Sciences, University of Helsinki, Helsinki, Finland
c Laboratory of Nanotechnology, University of Castilla-La Mancha, Aalmadén, Spain
Hemicelluloses are a group of polysaccharides abundant in the plant cell wall. They
could be obtained in large quantities as by-products in industrial pulping processes, due
to which they offer a sustainable and biodegradable alternative to conventional raw
materials. Hemicelluloses can be used to form aerogels, which are highly porous and
lightweight materials produced from hydrogels by removing the liquid phase. They
have potential for various applications from mechanical load bearing elements to
advanced materials with the capability of active sorption or releasing of desired
components (Mikkonen et al. 2013a). In composite materials, hemicelluloses usually
build a soft matrix, that can be reinforced for instance by cellulose fibrils.
Nanofibrillated cellulose (NFC), which consists of separated cellulose fibrils with
excellent mechanical properties and which is already a gel-like material in its original
hydrated state, represents a suitable option for this purpose.
In this study, aerogels and films were prepared from the hemicellulose
galactoglucomannan (GGM) and NFC, using ammonium zirconium carbonate (AZC) as
a cross-linker (Mikkonen et al. 2013b) in some of the samples. The aerogels were
prepared by lyophilization and the films by casting and drying at 23°C and 50% RH.
The composite materials were characterized with atomic and ultrasonic force
microscopy (AFM and UFM) in order to better understand the interactions between the
different components and to possibly link them to the sample morphology and their
macroscopic properties. In addition to the topography of the sample surface, provided
by conventional AFM also, UFM is able to yield a map of the elastic response of the
material in nanoscale (Cuberes 2009a).
GGM/NFC composite films with different amounts of the cross-linker AZC were
imaged with contact-mode AFM and UFM. The high-frequency ultrasonic vibration
used to produce the UFM images was induced to the sample from below. The images
showed mixed structures formed by stiff fibrils and granular units, which were
embedded in a softer matrix. In UFM, darker contrast indicates a softer area, whereas
stiffer areas appear brighter (Figure 1a). The size of these units varied around 100 nm,
except for the fibrils, that were larger in the longitudinal direction.
Similar granular structures were also observed on the surface of the aerogels, which
were imaged with tapping-mode AFM (Figure 1b). Attempts to image the aerogels in
contact-mode AFM were not successful, and hence UFM could not be applied in those
samples. Still, alternative ultrasonic-AFM methods such as intermittent-contact
heterodyne force microscopy (Cuberes 2009b) might provide the desired information.
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Links between the observed structural features of the composites and their macroscopic
properties will be discussed in the presentation. Special attention will be paid to the role
of the cross-linker AZC, with supporting data from other experiments.
Figure 1: (a) UFM image of a NFC/GGM film and (b) derivative of a tapping-mode AFM image of
the surface of a NFC/GGM aerogel (right).
References
Cuberes, M.T. (2009a). Mechanical-diode mode ultrasonic force microscopies. Book
chapter in “Applied Scanning Probe Methods XI”, Bhushan, B. and Fuchs, H.
(ed.), Springer-Verlag Berlin Heidelberg, 39-68.
Cuberes, M.T. (2009b). Intermittent-contact heterodyne force microscopy. Journal of
Nanomaterials, 2009, Article ID 762016 (doi:10.1155/2009/762016).
Mikkonen, K.S., Parikka, K., Ghafar, A. and Tenkanen, M. (2013a). Prospects of
polysaccharide aerogels as modern advanced food materials. Trends in Food
Science & Technology, 34(2), 124-136.
Mikkonen, K.S., Schmidt, J., Vesterinen, A.-H. and Tenkanen, M. (2013b).
Crosslinking with ammonium zirconium carbonate improves the formation and
properties of spruce galactoglucomannan films. Journal of Materials Science,
48(12), 4205-4213.
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Microscopic characterization of organic-inorganic hybrid nanosystems
Jokin Hidalgoa, Soledad Peresin
b, Alvaro Tejado
a
aInnovative and Sustainable Materials, Tecnalia Research & Innovation (Spain)
bFunctional Fibre Products Cluster, VTT (Finland)
The establishment of a new bio-based industry largely depends on the development of
new value-added products based on cellulose, by far the most abundant biopolymer on
Earth. In line with this, an intensive research has been carried out over the last decade
on nanostructured cellulose products, often combined with inorganic nanocompounds,
with the potential of being used in a wide range of valuable applications (biomedical
devices, polymer reinforcements, flexible electronic substrates, construction
components…). In parallel, the availability of large volumes of nanocellulose at
moderate cost is rapidly progressing with the setting-up of pilot-scale and commercial
facilities. The market for these products will be growing millions of euros by 2020
(Future Markets 2014).
In the frame of this “Short Term Scientific Mission” a preliminary microscopic study of
organic-inorganic hybrid nanocomposites was carried out using Scanning Electron
Microscopy (SEM) and Atomic Force Microscopy (AFM) on different substrates. Three
different types of cellulose substrates (Fig. 1), i.e. cellulose microfibres (MFC),
cellulose nanofibres (NFC) and highly oxidized cellulose (HOC), the latter prepared as
reported elsewhere (WO2012119229A1, Tejado et al. 2012), were combined with 3
types of inorganic nanoparticles, namely titanium dioxide (TiO2), sodium
montmorillonite (MTM) and organically modified montmorillonite (OMTM).
Figure 1: SEM images of MFC (left), NFC (centre) and HOC (right) at the same magnification level
The stability of suspensions were initially evaluated and critically correlated with the
quality of the films formed via casting or vacuum filtration. Remarkably, while MTM
always gave rise to stable suspensions and good quality films, TiO2 caused severe
flocculation of NFC and HOC, showing identical behaviour to OMTM. Subsequently,
microscopic analyses confirmed those floc-promoting interactions (Fig. 2) and also
succeeded in characterizing different features of the samples, such as the well-defined
profile height differences, the disintegrating effect of sonication on HOC sample or the
homogeneous formation of OMTM nanoparticle layer on MFC substrate.
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Figure 2: SEM image of NFC/OMTM hybrid with detail of a clay aggregate
This STSM has a provided a better understanding over the structure of organic-
inorganic hybrid systems made of nanocellulose films and TiO2/nanoclay, especially on
the processability problems that may arise within the production of this type of hybrids.
References
Future Markets (2014). The global market for nanocellulose to 2020, p. 85. Retrieved
from http://www.futuremarketsinc.com/index.php/nanoreports-63/nanocellulose
Tejado, A., Alam, N.Md., Antal, M., Yang, H. and van de Ven, T.G.M. “Energy
requirements for the disintegration of cellulose fibers into cellulose nanofibers”,
Cellulose 19, 831-842 (2012)
Van de Ven, T.G.M., Alam, N.Md., Antal, M. and Tejado, A. “Highly charge-group
modified cellulose fibers which can be made into cellulose nanostructures or
super-absorbing cellulosic materials and method of making them”,
WO2012119229A1
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Effect of raw material and pulping conditions on dissolved kraft lignin;
characterization of kraft lignins from pine, spruce and eucalyptus by
elemental analysis and analytical pyrolysis
Olena Sevastyanovaa, Galina Dobele
b, Vilhemina Jurkjane
b, Antonia Svärd
a,
Elisabet Brännvalla
a Royal Institute of Technology, KTH, Fiber and Polymer Technology, Stockholm,
Sweden,
b Latvian State Institute of Wood Chemistry, Riga, Latvia
Lignin is one of the main biopolymers in plants and is abundantly accessible and easily
available. The current challenge is to meet the need for energy and raw materials, and
reform to a more environmentally sustainable society and lignin has a potential to play
an important role to meet this challenge. During the kraft pulping process are lignin is
degraded and dissolved into the cooking liquor and burned for energy in the process.
The pulping conditions used today are aimed at obtaining high-quality pulp as the main
goal. However, lignin has structural properties allowing it to be a starting material for
chemical modification leading to the preparation of valuable polymeric materials and
chemicals form phenol. Detailed characteristic of lignin samples depending on the
pulping conditions will provide future opportunity to adjust the pulping process with
regards to pulp properties and with respect to obtain lignin with desired characteristics.
Previous studies on kraft lignin characterization has focused on the understanding of the
kraft pulping reactions. (Gellerstedt and Lindfors 1984) More recent studies to use kraft
lignin for value added products has focused on comparing different technical lignins
obtained through different puling methods. (Mansouri and Salvado 2009; Prinsen et al.
2013) In the present study, wood chips of pine, spruce and eucalyptus were pulped with
the kraft process with constant temperature similar alkali and sulphidity to different
cooking times, see table 1.
Table 1: Pulping conditions
NaSH
[M]
NaOH
[M]
Liquor-to-wood
ratio, l/kg
Cooking
temperature, ⁰C
Cooking time, min
Pine 0,26 1,2 4 157 100, 200 260
Spurce 0,26 1,2 4 157 100, 200, 260
Eucalyptus 0,26 1,0 4 157 30, 60, 100
From the collected black liquor the dissolved kraft lignin was precipitated by
acidification with sulphuric acid. The collected lignin samples were analysed with
regards to composition with analytical pyrolysis, Py-GC/MS and elemental analysis
(CHNS). Figure 1 depicts the lignin and carbohydrate composition determined by
analytical pyrolysis. The amount of lignin is higher for pine and spruce compared to
eucalyptus, Figure 1A. However, the lignin- carbohydrate ratio varied little more with
pulping time for the softwood lignin samples compared with the eucalyptus lignin
samples, see figure 1B.
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A B Figure 2: Composition of lignin samples obtained with analytical pyrolysis, A. Variation of the
lignin carbohydrate ratio depending on cooking time, B.
The sulphur content, and especially the organically bound sulphur, in kraft lignin is one
of the most problematic factors for possible applications. Both the elemental analysis
and the analytical pyrolysis provided information of the amount of sulphur in the lignin
samples, see figure 2. Both analytical methods showed that the eucalyptus lignin
samples had the highest sulphur content compared to the pine and spruce lignin
samples. The amount of sulphur in the lignin samples varied little with pulping time.
References
Gellerstedt, G.; Lindfors, E. (1984) Structural changes in lignin during kraft pulping.
Holzforschung, 38, 151.
Prinsen, P.; Rencoret, J.; Gutierrez, A.; Liitiä, T.; Tamminen, T.; Colodette, J.; Berbis,
A.; Jimenez-Barbero, J.; Martinez, A.; del Rio, J. (2013) Modifcations of the
lignin structure during alkaline delignification of eucalyptus wood by kraft, soda-
AQ, and soda-Oa cooking. Ind Eng Chem Res., 52, 15702.
Mansouri, N.; Salvado, J. (2006) Structural characterization of technical lignins for the
production of adhesives: Application to lignosulfonate, kraft, soda-anthraquinone,
organosolv and ethanol process lignins. Industrial Crops Products, 24, 8
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
60 100 100 200 260 100 200 260
Eucalyptus Pine Spruce
Chemical composition based on Py-GC/MS
Others, %
Cabohydrates, %
Lignin derivates, %
0
1
2
3
4
5
6
7
8
9
10
60 100 100 200 260 100 200 260
Eucalyptus Pine Spruce
Sulf
ur
con
ten
t, %
Elemental analysis Py-GC/MS
Figure 3: Sulphur content in lignin samples determined by Py-GC/MS and elemental analysis
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University of Coimbra, DEQ & DCV
Treatment of pulp in a kneader and disperger
Johannes Leitner, Technical University of Graz, Institut for Paper-, Pulp and Fiber
Technology.
Compared to classical laboratory PFI refining, kneading is a very gentle type of fiber
treatment that results in curled, kinked and microcompressed fibers. Page et al. (1984)
summarized the mechanisms of creating fiber damages such as curl, kink, axial fiber
dislocations and fibrillation. These fiber damages positively affect the tensile
deformability (Page 1966).
More recently, Leonhardt (2003) investigated the creation of fiber damages by a
kneader under pressurized conditions. This contribution presents the first preliminary
results from laboratory kneading below 100 °C on various fiber damages.
Classical equipments that are industrially used in waste paper recycling processes were
used in this study: a laboratory kneading disperger and an equipment similar to a disk
disperger. Both types of equipments operate at different treatment speeds where the
kneading disperger was operated at max. 60 rpm for up to 30 minutes and the disk
disperger was operated at max. 1200 rpm for up to 2 minutes. The effects of
temperature [20, 45, 65, 80 and 100°C] and consistency [25 and 35%] were verified.
Figure 1: Effects of pulp consistency on the average fiber curl and Shopper Riegler dewatering.
The preliminary results in Figure 1 show a significantly positive effect of the pulp
consistency on the average fiber curl. At an initial consistency of 35%, the fiber curl
was linearly increased to roughly 23%, however, pulp at 25% inlet consistency showed
a decline in curl already at 1000 revolutions. An interesting phenomenon was observed
when pulp of the higher consistency was kneaded for a longer time (e.g. 2 minutes at
1200 rpm). The Shopper Riegler initially increased but then declined at higher
revolutions. This was attributed to the design of the disk disperger. Since the disperger
was open during the treatment, the generated heat evaporated the free water and thus
severely increased the consistency during the treatment up to 58%. After 2400
revolutions, the pulp resembled a harshly deflaked fiber material prior to a flash dryer.
The pulp had a knodular structure which most likely requires a more intensive
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University of Coimbra, DEQ & DCV
disintegration. However, the lower consistency did not show such an intensive increase
in dry content and might be interesting when a higher degree of beating is needed.
Figure 2 provides results from kneading of preheated pulp at 80°C. The kneader yielded
in a significantly faster increase in the average fiber curl when compared to the
disperger at similar revolutions. However a longer dwell time resulted in only in a small
increment in fiber curl. It appears that the consistency also plays a minor role. Kneading
seems also to be also gentler in terms of the dewatering resistance. The Schopper-
Riegler was increased to a very small extent.
Figure 2: Effects of pulp consistency in the kneader at 80°C on the average fiber curl and Schopper Riegler
dewatering.
References
Leonhardt W. (2003). Faserumformungen beim Kneten im „Hochtemperaturbereich’’.
Wochenbl. Papierfabrikation 131(3), 88-93.
Page D.H. (1966). The axial compression of fibres - a newly discovered beating action.
Pulp Paper Mag. Can., 67(1), T2-T12.
Page D.H., Barbe M.C., Seth R.S., Jordan B.D. (1984). The mechanism of curl
creation, removal and retention in pulp fibres. J. Pulp Pap. Sci. 5, J74–J79.
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University of Coimbra, DEQ & DCV
Conversion of wood particles to cellulose fibers during a modified
acetosolv process Fabian Herz
1, Arnis Treimanis
2, Andrzej Majcherczyk
1, Ursula Kües
1
1Dept. of Molecular Wood Biotechnology and Technical Mycology, Büsgen-Institute,
Georg-August-Universität Göttingen, Germany
2Cellulose Laboratory, LS Institute of Wood Chemistry (LSIWC), Riga, Latvia
Bioethanol is currently produced by fermentation of sugars derived from annual crops,
specifically corn or sugarcane. Compared to 1st generation biofuels from agricultural
crops, production of bioethanol from non-food materials such as wood lignocellulose
appears to be energetically more favorable with positive ecological and socio-economic
aspects. However, thermo-chemical dissociation of lignocellulosic material and removal
of lignin is necessary to make wood cellulose accessible for enzymes hydrolyzing it to
glucose. Fast growing hardwoods, such as poplar and willow, from short-rotation
forestry (SRF) sites have high cellulose contents (50-55%). A modified acetosolv
process was applied at moderate temperatures to produce fibers suitable for efficient
enzymatic hydrolysis of cellulose to glucose with high conversion yields. Importantly,
the modified acetosolv process preserves the wood cellulose of hardwoods almost
completely in fiber and fiber fragment form. Despite the remaining 5% lignin, the
cellulose can be converted to glucose with about 90% yield using commercially
available hydrolytic enzymes.
The goal of this short-term scientific mission at LSIWC was to study wood cell wall
structure and fiber composition changes during this modified acetosolv process
developed in Göttingen. The main focus was to analyse the conversion of wood (mainly
hardwood) to cellulose fibers during chemical treatment and to study the conversion
mechanism. Modified Acetosolv treatment was stopped at specific time-points to
produce (T0=0 min, T1=15 min, T2=30 min, T3=60 min, T4=90 min and T5=120 min)
different conversion stages from wood particles to cellulose fibers. Changes in wood
particle structure were clearly observed by SEM starting around T2 of treatment. At T3
> 90% of the fibers are separated and no enhancements in fiber detachment can be
observed with increasing treatment time (T4 and T5). Via L&W Fiber Tester the length
of the fibers decreases due to extended chemical treatment and partial dissolution of
lignin and hemicelluloses. Short-rotation wood (poplar and willow) fiber length
reduction exceeds more than 0.1 mm for treatment between time-points T2 and T4.
Changes in composition where obtained via FTIR especially in lignin yield, sugar
composition and degree of acetylation. With increasing treatment times lignin yield
decreases form T0=23.9% to T5=3.2%. Sugar composition changed due to
hemicellulose extraction during modified acetosolv process.
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4. Posters
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University of Coimbra, DEQ & DCV
Microwave ionic liquid activation coupled with mAb macroarray
detection as a rapid and easy tool kit for polysaccharides analysis.
Idelette Plazanet1, Sabine Lhernuold
1, Christian Breton
2, Rachida Zerrouki
1, Guy
Costa1
1Laboratoire de Chimie des Substances Naturelles (EA 1069) Faculté des Sciences et
Techniques 123 Avenue Albert Thomas F-87060 Limoges Cedex France Tel : 33 (0)
555 457 393 Fax : 33 (0) 555 457 386 http://www unilim fr/lcsn 2Unité INRA d’Amélioration de Génétique et de Physiologie Forestière 2163 avenue de la
pomme de pin Ardon CS 40001 45075Orléans cedex 2 France Tel : 33 (0) 238 417 824 Fax : 33
(0) 238 414 809 http://www orleans inra fr
Ionic liquids (ILs) have been extensively used as a polymer solvent for biofuel
experiments. Here, we propose to use ILs not only to breakdown wood cell wall but also
to determine the polysaccharide molecular composition of the timber wall.
Polysaccharides from walnut wood have been extracted by a sequential proceeding or
dissolved by ILs before being spotted on nitrocellulose membrane and hybridized
against mAb. Polysaccharide fingerprints previously solubilized by the IL are consistent
with those of the sequential proceeding. Thus the breakdown of woody biomass by IL
that releases polysaccharides represents a new method for studying these molecules and
replaces conventional cell wall polymer extraction processes which are time and
material consuming.
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University of Coimbra, DEQ & DCV
Morphological ultrastructural characteristics of fines fraction
produced during HC and LC refining of TMP for fundamental
understanding of property development
Dinesh Fernando and Geoffrey Daniel
Department of Forest Products, Swedish University of Agricultural Sciences (SLU), P.O. Box
7008, SE-750 07 Uppsala, Sweden.
Wood fibres respond differently to industrial mechanical pulping (MP) processes
depending on operating parameters like energy input, refining temperature, consistency
etc. and because of inherent fibre characteristics. These responses are reflected
primarily by changes/alterations to the native fibre structure that can occur at any of the
fibre hierarchical structure levels ranging from molecular, nano, ultra to micro-structure.
During processing, cell walls of fibres fibrillate differently releasing parts of the fibre
wall (e.g. flake-like particles from the outer compound middle lamella and S1, long
ribbon-type fibrils from the inner S2 layer, remnants from bordered-pits etc.) forming
the fines fraction of a given pulp.
Mechanical pulps can consist of ca 30% fine particles (fines) thereby emphasizing its
importance for a given pulp where they contribute significantly to strength- and optical
properties of final paper products. Thus it is of great importance to focus research not
only on process property relationships but also on basic studies for understanding
fundamental mechanisms at the fibre level including particle development during
different industrial processes (e.g. thermomechanical pulp (TMP) refining). In this
study, we have investigated the effects of low-consistency (LC) and high-consistency
(HC) refining of TMP on the development of the fines fraction concerning
morphological ultrastructural characteristics using scanning electron microscopy
(SEM).
Morphological characteristics of fine particles produced during LC-refining differed
significantly to that of HC-refined pulps. Differences were directly related to the fibre
development mechanisms revealed previously during two refining processes (Fernando
et al. 2013). HC refining generated a wide range of morphologically dissimilar long
ribbon fibrils that dominated the fine fraction of the pulp. HC refining produced typical
fibrillar fines existing in a wide range of thin thread/string-like microfibrils, aggregates
of macrofibrils and wider sheet-like fibrils and lamellae sheets from the fibre S2 layer of
the fibre cell wall. Conversely, LC refining produced primarily string/thread-like narrow
long fibrils as particles of the fine fraction and lacked the much broader sheet-like and
lamellar sheet fibrils. In addition, flake-like particles from the outer fibre wall layers
were commonly observed in second stage LC compared to third stage LC refining and
they decreased in relative amounts with energy input, a feature also seen for both HC
and LC pulp types. High-throughput image-based investigations using automated
fluorescence microscopy combined with image analysis showed quantitative differences
in morphological properties between fines from the same low and high consistency
refined pulps (Hafrén et al. 2014) corroborating results obtained from SEM
observations. The morphological characteristics of fines from the two processes explain,
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University of Coimbra, DEQ & DCV
at least partly, some of the physical and optical properties developed by the pulps.
Present results provide further evidence strongly supporting the hypothesis of the
different refining and fibre development mechanisms proposed earlier for HC- and LC
processes (Fernando et al. 2013).
References
Fernando, D., Gorski, D., Sabourin, M., Daniel, G. (2013). Characterization of fibre
development in high and low consistency refining of mechanical pulp.
Holzforschung, 67(7), 734-745.
Hafrén, J., Fernando, D., Gorski, D., Daniel, G., Salomons, F.A. (2014). Fiber and fine
fractions-derived effects on pulp quality as a result of mechanical pulp refining
consistency. Wood Sci Tech. (under review).
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University of Coimbra, DEQ & DCV
Effect of chemical-physical treatments on a lignocellolosic biomass
properties and solubility Stefania Angelini, Pierfrancesco Cerruti, Barbara Immirzi, Mario Malinconico,
Gabriella Santagata, Gennaro Scarinzi
Institute of Polymer Chemistry and Technology (ICTP-CNR), Via Campi Flegrei 34, 80078
Pozzuoli (NA), Italy
Ligno-cellulosic biomass is a multi-component material of the vascular plants cell wall.
It is the most abundant and renewable organic substance on earth. It is chemically
composed of a carbon-oxygen framework that includes aliphatic, methoxyl, phenolic
and hydroxyl moieties. A large amount of this biomass is generated from the paper
industries as by-product in the pulping and bleaching processes of wood pulp and from
the biorefineries. In this communication lignocellulosic raw material (LRR) supplied as
by-product of the second generation bioethanol fermentative production process is
characterized and deconstructed. Moreover the deconstruction products are employed as
fillers in PHB polymeric matrix in order to obtain biocomposites suitable for a wide
range of applications.
The spectroscopic characterization of LRR was carried out through ATR-IR and solid-
state 13C MAS-NMR. Both the spectroscopic data showed that the material, after the
fermentative production process, still contains polysaccharidic moieties. The NMR
spectrum of LRR showed that the biomass contained both lignin and cellulosic matter.
This was indicated by typical sharp cellulose signals of C–1 at 105.2 ppm, C– 2,3,5 at
72.5 and 75.1 ppm; C–4 at 84.0 and 89.0 ppm; C–6 at 63.5 and 65.2 ppm (Freitas et al.
2001).
These results were confirmed by the chemical characterization, performed on LRR, in
order to evaluate acid-insoluble lignin (KL) and holocellulose (HC) contents, through
the Klason and the sodium chlorite methods respectively.
The deconstruction of the biomass was carried out through a physical-mechanical
treatment based on ball-milling for different times in order to evaluate its effect on the
LRR structural and processability properties. The ball milling process was followed by
ATR-IR spectroscopy. The ATR-IR analysis showed that the absorptions relative to the
crystalline fraction of HC completely disappeared (Schwanninger et al. 2004). This was
attributed to the amorphization of HC, which improved the solubility and the
workability of the material.
Therefore solubility tests were performed on the milled materials through the
dissolution in DMSO/NMI (Fig. 1). The figure shows that, increasing the ball milling
time, the material solubility is enhanced.
Work is in progress to characterize the soluble fraction of milled material through ATR-
IR, 13C MAS-NMR and GPC. The effect of milled LRR on the properties of
43
University of Coimbra, DEQ & DCV
biocomposites will be evaluated through rheological and mechanical characterization.
Biocomposites containing HC and KL will be also prepared with the aim to assess their
specific effect on the materials properties.
References
Freitas, J.C.C., Bonagamba, T.J. and Emmerich, F.G. (2001). Investigation of biomass-
and polymer-based carbon materials using 13C high-resolution solid-state NMR.
Carbon, 39, 535–545.
Schwanninger, M., Rodrigues, J.C., Pereira, H., Hinterstoisser, B. (2004). Effects of
short-time vibratory ball milling on the shape of FT-IR spectra of wood and
cellulose. Vibrational Spectroscopy, 36, 23–40.
Zhang, A., Lu, F., Sun, R.-C. and Ralph, J. (2010). Isolation of Cellulolytic Enzyme
Lignin from Wood Preswollen/Dissolved in Dimethyl Sulfoxide/N-
Methylimidazole. Journal of Agricultural and Food Chemistry, 58, 3446-3450.
44
University of Coimbra, DEQ & DCV
Sample preparation for measurement of fibre-fibre wet friction
Seyed Kourosh Latifi, Pooya Saketi, Pasi Kallio, Micro- and Nanosystems Research
Group, Department of Automation Science and Engineering, Tampere University of
Technology, Tampere, Finland
Interfibre friction force is an important factor in papermaking as it plays a role in
holding the web together and thus, influencing runnability. The objective of this
research is to develop a methodology using microrobotics to prepare fibre samples for
direct measurement of the friction force between two individual pulp fibres. In the next
phase, Piezo-based force measurement (surface scanning) will be implemented to
investigate the friction force between fibres.
Most of the studies on fibre friction have been performed in textile field on cotton and
synthetic fibres. Mizuno et al. 2006 [1] applied scanning probe microscope (SPM) for
the friction measurement between two polyester fibres. The challenging step in this
measurement was attaching the polyester fibre to the cantilever with epoxy glue. In
comparison with polyester fibres, measuring friction forces between pulp and paper
fibres is more challenging than between synthetic fibres, since pulp fibres are very
irregular both on the surface and in the cross section. Since pulp fibres are few
millimetres in length and few micrometres in diameter, sample preparation and
measurement of fibre-fibre friction become more challenging. The atomic force
microscope (AFM) has been used in recent years for friction studies. Zauscher and
Klingenberg 2001 [2] utilized colloidal probe microscopy to study sliding friction
between model cellulose surfaces in aqueous solutions. Huang et al. 2009 [3]
implemented AFM to investigate interfibre friction force for pulp fibres. They
concluded that AFM is an effective tool for measuring micro-scale interfibre friction
forces. However, in sample preparation procedure for AFM, assembly of fibre to AFM
cantilever is costly and time-consuming, and there is the risk of making the top surface
of fibre segment contaminated with adhesive. Furthermore, AFM calibration should be
performed for every fibre segment attached to the cantilever. Moreover, AFM is not
appropriate for high throughput experiments.
In this research, Universal Surface Tester (INNOWEP GmbH, Germany) will be used
for measurement of interfibre wet friction. Measurement method is illustrated
schematically in Fig 1.
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University of Coimbra, DEQ & DCV
The microrobotics platform developed by Saketi et al. 2012 [4] is used for preparing the
samples for measuring friction between individual wet fibres. The challenge is
mounting morphologically complex fibres, which are tens of micrometres in diameter,
on a solid surface using adhesives without contaminating the surface of the fibre. In
order to assure that the fibres are in contact with each other during the test, the height of
the adhesive material should be only a couple of micrometres. Two series of samples
are required for wet friction experiments. The first group of samples are prepared on a
rigid substrate. Fig 2 shows a micro-stage fabricated using SU-8 and UV-lithography on
a Silicon wafer. Next, UV curable glue is spun on the silicon wafer to make the SU8
surface sticky. Spinning is applied to distribute the glue uniformly on the micro-stage
down to few micrometres in height. Finally, the microrobotic platform [4] is used for
straightening and positioning the fibres on the micro-stage (Fig 2).
The second group of samples are prepared on a rigid semi-sphere substrate. To cover
the ball surface with adhesive, UV curable glue is distributed on the ball surface by
spinning. Afterwards, the microrobotic platform is used for straightening and
positioning the fibres on the ball surface (Fig 3). Samples on the ball tips will be used as
the top fibre in fibre-fibre wet friction measurement.
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University of Coimbra, DEQ & DCV
References
[1] Mizuno, H., Kjellin, M., Nordgren, N., Petterson, T., Wallqvist, V., Fielden, M.,
Rutland, M.W., (2006). “Friction measurement between polyester fibres using the fibre
probe SPM”. Australian Journal of Chemistry 59(6) 390–393.
[2] Zauscher, S., Klingenberg, D.J., (2001). “Friction between cellulose surfaces
measured with colloidal probe microscopy”. Colloids and Surfaces A: Physicochemical
and Engineering Aspects 178 213–229.
[3] Huang, F., Li, K., Kulachenko, A., (2009). “Measurement of interfibre friction force
for pulp fibres by atomic force microscopy”. Journal of Materials Science. 44:3770–
3776.
[4] Saketi, P., Von Essen, M., Mikczinski, M., Heinemann, S., Fatikow, S., Kallio,
(2012). ”A flexible microrobotic platform for handling microscale specimens of fibrous
materials for microscopic studies”. Journal ofMicroscopy, Vol. 248, Pt 2 2012, pp. 163–
171.
47
University of Coimbra, DEQ & DCV
Reinforcement paper with nanofibers using eucalyptus pulp as raw
material
Iñaki Urruzola, Eduardo Robles, Luis Serrano, Jalel Labidi, Chemical and
Environmental Engineering Department, University of the Basque Country, Plaza Europa, 1.
20018. Donostia-San Sebastián, Spain. [email protected]
In recent years, the study of cellulose has been increased, as it is the most
abundant organic biomolecule available, with a production that reaches over 100
million tons in plants around the world. (Fratzl 2003; Vincent 1999; Bidlack et al. 1992;
Samir et al. 2005).
The obtaining of cellulose nanofibers has attracted significant interest in the last
few decades due to the unique characteristics they endow, such as high surface area to
volume ratio, high surface area, high Young’s modulus, high tensile strength, and low
coefficient of thermal expansión (Nishino et al. 2004) and due to the potential of
cellulose in several applications. Chemical and mechanical treatments have been used to
obtain cellulose nanofibers and nanocrystals using bleached eucalyptus pulp as raw
material. High pressure homogenization has been applied to obtain nanofibers.
Cellulose nanocrystals have been obtained with the combination of hydrolysis and
homogeneization treatments. Obtained materials have been characterized by FTIR,
TGA, AFM and XRD. Paper was elaborated by hot pressing and reinforced with
eucalyptus cellulose fibers using different concentration of nanofibers and nanocrystals.
The mechanical properties (Table 1) of the reinforced papers were compared to those of
regular micropaper.
Table 1: mechanical properties of reinforced papers
Load(N) Tensile Stress
(MPa) Strain (%) Modulus (GPa)
reference 6.27 ± 1.46 14.01 ± 3.73 1.13 ± 0.34 1318.92 ± 437.85
0.5% nanofibers 6.22±1.74 13.37 ± 2.88 1.18 ± 0.39 1162.78 ± 166.25
1% nanofibers 4.97 ± 1.38 12.89 ± 2.86 1.17 ± 0.30 1126.22 ± 414.46
2% nanofibers 8.75 ± 1.60 17.19 ± 2.69 1.02 ± 0.25 1637.05 ± 184.55
5 % nanofibers 10.77± 2.92 23.54 ± 5.64 1.33 ± 0.34 1606.58 ± 431.25
0.5 % nanocrystals 6.74 ± 1.74 13.27 ± 2.27 1.56 ± 0.28 886.77 ± 105.46
1% nanocrystals 9.51 ± 1.57 16.78 ± 1.46 1.86 ± 0.20 914.80 ± 155.06
2% nanocrystals 11.94 ± 3.97 20.32 ± 5.65 2.00 ± 0.57 1031.40 ± 158.20
5% nanocrystals 17.53 ± 3.80 25.05 ± 4.63 2.16 ± 0.38 1160.04 ± 71.71
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University of Coimbra, DEQ & DCV
References
Bidlack J, Malone, M, and Benson R. Molecular structure and component integration of
secondary cell walls in plants, Proc. Oklahoma Acad. Sci. 72 (1992) 51-56.
Fratzl, P. Cellulose and collagen: From fibres to tissues, Curr. Opin. Colloid. Interface
Sci. 8 (2003) 32-39.
Nishino T., Matsuda I., Hirao K., All-cellulose composite, Macromolecules 37 (2004)
7683–7687.
Samir M, Alloin, F, and Dufresne, A., Review of recent research into cellulosic
whisker, ther propieties and ther application nanocomposites field,
Biomacromolecules, 6 (2005) 612-626.
Vincent, J. F., from cellulose to cell, J. Exp. Biol. 202 (1999) 3263-3268.
49
University of Coimbra, DEQ & DCV
Influence of the lignocellulosic strcuture on the kinetic model of
enzymatic hydrolysis
Ivo Valchev, Stoyko Petrin, Nikolay Yavorov, University of Chemical Technology and
Metallurgy, 8, KL. Ohridski Blvd., 1756, Sofia, Bulgaria.
The inhomogeneous distribution of cellulose, hemicelluloses and lignin as well as the
difference in its structure throughout the pulp matrix make the classical rate equation of
Michaelis-Menten inadequate to describe the kinetics of enzyme catalysed hydrolysis
(Baley 1989 and Chrastil 1988a). That model is not suitable for the analysis of
enzymatic reactions of heterogeneous system. The alternative approach suggests that the
initial hydrolysis velocity should be expressed as a function of the initial enzyme
concentration. The accessibility of substrates to enzymes depends on the structural
features of the substrate including cellulose crystallinity, degree of cellulose
polymerization, surface area, and content of lignin.
The objective of the study is to determine the relationship between fibres structural
features of the lignocellulosic materials and the kinetic mechanism of the enzymatic
hydrolysis.
Cellulasic hydrolysis is a hurdle because of the heterogeneous nature of the cellulose
substrate and because degradation of the cellulose chain progresses in only one
direction for each cellobiohydrolase, effectively reducing the reaction to a one-
dimensional process. As known, cellulose consists of relatively easily accessible
amorphous regions with few lateral interactions among the cellulose chains, as well as
of crystalline domains much more difficult to hydrolyze. The exponential kinetic
equation provides a good interpretation of the kinetics of cellulase hydrolysis of
different agricultural lignocellulosic materials (wheat straw and maize stalks) and
cellulase treatment of pulp for beating efficiency improvement (Radeva et al. 2012,
Radeva et al. 2009). The exponential kinetic equation is valid for processes taking place
on uniformly inhomogeneous surfaces and successfully applied in studies of enzymatic
hydrolysis. According to the model of uniformly inhomogeneous surfaces, the active
centers on the surface are distributed linearly, referring to their energy and entropy. The
exponential kinetic equation is applied in the form (Equation 1):
a
evv
0
(1)
where the dimensionless quantity α is a degree of hydrolysis, v = dα/dt and v0 are the
current and the initial rate of enzymatic hydrolysis, respectively. The kinetic coefficient
of inhomogeneity a accounts for the energy and the entropy inhomogeneity of the
system. The approximate integral form of Equation 1 is used for determination of the
kinetic paramiters (Equation 2):
ta
ava
ln1
)ln(1
0
(2)
The exponential equation does not show quite good results in the extended cellulase
hydrolysis of steam-exploded wood. In that case the topochemical model is valid and
the hydrolysis rate depends on the number of reactive sites, formed at the beginning of
the process, and the growth rate of the transformed from these reactive sites. The rate of
progress of the reaction is determined by the size of the interface between the reacted
and unreacted solid.
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University of Coimbra, DEQ & DCV
Kinetic studies with different xylanase preparations show quite good results when the
modified topochemical Prout-Tompkins equation is used (Valchev et al. 1998, Dimitrov
et al. 2005). Xylanases are the most commonly used enzymes in pulp bleaching. The
nature of the substrate and its location in pulp suggest application of a topochemical
mechanism is more appropriate.
According to this model, the rate of hydrolysis v is a function of the amount of product
that subsequently becomes soluble (degree of hydrolysis) α and of the amount of
residual undissolved substrat at any time (1 - α) (Equation 3):
11
)1(
kdt
dv (3)
where k is the rate constant. The power factors (χ – 1)/ χ and (χ + 1)/ χ determine the
relative contributions by the dissolved and undissolved parts of the substrat,
respectively to the rate of hydrolysis. Based on this topochemical mechanism, the rate
of delignification depends on the size and the state of the changing reaction interface.
The integrated form of Equation 3 used for the description of the experimental data is:
tk .
11
(4)
where k1 = k/χ is an apparent rate constant and χ is a power factor.
The presented study shows that the structural features of the lignocellulosic material are
the controlling factor on the type of the kinetic mechanism. The topochemical model
provides a good interpretation of cellulase hydrolysis of steam-exploded wood while the
exponential equation is applied for agricultural lignocellulosic materials.
References
Baley, D. (1989). Enzyme kinetics of cellulose hydrolysis. Biochemical Journal, 262,
1001–1002.
Chrastil, J. (1988a). Enzymatic product formation curves with the normal or diffusion
limited reaction mechanism and in the presence of substrate receptors. International
Journal of Biochemistry, 20, 683–693.
Valchev, I., Yotova, L., Valcheva, E. (1998). Kinetics of xylanase treatment of
hardwood pulp. Bioresource Technology, 65, 57-60.
Dimitrov, I., Valchev, I., Valcheva, E. (2005). Topochemical kinetics of xylanase action
on kraft pulp. Biocatalysis and Biotransformation, 23(1), 33-36.
Radeva, G., Valchev, I., Petrin, S., Valcheva, E., Tsekova, P. (2012). Kinetic model of
enzymatic hydrolysis of steam–exploded wheat straw. Carbohydrate Polymers,
87(2), 1280-1285.
Radeva, G., Bikov, P., Valchev, I. (2009). Kinetic model of cellulase treatment of pulp.
ITALIC 5 Conference on lignocellulosic chemistry, Varenna, Italy, 129 -132.
Acknowledgments
The authors thanks for the financial help of Project BG051PO001-3.3.06-0038 funded
by OP Human Resources Development 2007-2013 of EU Structural Funds.
51
University of Coimbra, DEQ & DCV
Designed lignocellulose-based films for tunable physico-chemical and
spectral properties
Muraille L, Aguié-Béghin V, Paës G, Chabbert B., UMR FARE, INRA, University of
Reims Champagne-Ardenne, Reims, France
Gradual formation of the plant cell wall gives rise to a gradient polymer
organization which plays a key role in plant cell growth, and contributes to biological
and mechanical deconstruction. Owing to the large complexity and chemical variability
of the lignified cell walls, unravelling the molecular mechanisms that promote their
architecture, physicochemical properties and reactivity is still challenging. In order to
determine some of the interactions which are responsible for this architecture, model
systems inspired from the plant cell walls show great promises, because components are
carefully selected and can be assembled progressively. Such bioinspired systems can
provide information on the properties of plant cell walls but also on the mechanisms
involved in recalcitrance towards enzymatic or physicochemical destructuration, which
is a key problem in the lignocellulose biorefinery era [1, 2, 3]. In addition, designed
lignocellulosic polymer assemblies can provide high-performance materials deserving
several applications [4, 5].
Using controlled physical and/or enzyme-mediated assembly, we have designed
different bioinspired lignocelluloses films containing cellulose nano-crystals,
hemicellulose and lignin with various concentrations. As revealed by the water sorption
isotherms, the films exhibited different hygroscopic properties which mostly depend on
their composition and the way of assembly. Notably, these properties could be
modulated depending on controlled lignin introduction and phenolic cross-linkage in the
composites. Thus controlled organization of the lignocellulosic polymers can be
achieved in systems with various water content which was further shown to deeply
impact on spectral and mechanical properties of resulting films and on the mobility of
fluorescent probes using FRAP.
References
[1] Martin-Sampedro, R., Rahikainen, J.L., Johansson, L.S., Marjamaa, K., Laine, J.,
Kruus, K., Rojas, O.J. Biomacromolecules, 14 (2013), 1231-1239.
[2] Paës, G., Chabbert, B. Biomacromolecules, 13 (2012), 206-214.
[3] Valentin, R., Cerclier, C., Geneix, N., Aguié-Béghin, V., Gaillard, C., Ralet, M.C.,
Cathala, B. Langmuir, 26 (2010), 9891-9898.
[4] Eichhorn, S.J., Dufresne, A., Aranguren, M., Marcovich, N.E., Capadona, J.R.,
Rowan, S.J., Weder, C., Thielemans, W., Roman, M., Renneckar, S., Gindl, W.,
Veigel, S., Keckes, J., Yano, H., Abe, K., Nogi, M., Nakagaito, A.N., Mangalam,
A., Simonsen, J., Benight, A.S., Bismarck, A., Berglund, L.A., Peijs, T. 2010. J.
Mater. Sci., 45(1), 1-33.
[5] Hambardzumyan, A., Foulon, L., Chabbert, B., Aguie-Beghin, V.
Biomacromolecules, 13 (2012), 4081-4088.
52
University of Coimbra, DEQ & DCV
Lignin modified porous BPA.DA-St polymers characterised by
thermal analysis
B. Gawdzik
a, M. Sobiesiak
a, B. Podkościelna
a, O. Sevastyanova
b,
aDEPARTMEN OF POLYMER CHEMISTRY, FACULTY OF CHEMISTRY, MARIA
CURIE-SKŁODOWSKA UNIVERSITY, PL. M. CURIE-SKŁODOWSKIEJ 5, 20-031
LUBLIN, POLAND bKTH, ROYAL INSTITUTE OF TECHNOLOGY, DEPARTMENT OF FIBRE AND
POLYMER TECHNOLOGY, SE-10044 STOCKHOLM, SWEDEN
Lignin with its chemical structure is very interesting substrate for production of
new materials. It can be equally precursor for preparation of carbon sorbents
(Myglovets et al. 2014), as well as reagent in synthesis of polymers.
This paper describes thermal properties of new polymers prepared by reaction of
bisphenol A glicerolate diacrylate (BPA.DA) with styrene (St) and a lignin component.
As the lignin component unmodified lignin (L), lignin esterified with acrylic acid (LA)
or lignin initially reacted with epichlorohydrin and then with acrylic acid (LEA) were
applied. Structure of monomers used in the polymer synthesis and its general scheme
are presented in Figure 1.
Figure 1: Structure of monomers and general scheme of the polymer synthesis.
Polymerisation was carried out as suspension-emulsion process. Mixture of the
monomers (BPA.DA, St and lignin component) with the initiator (AIBN) and pore-
forming diluents were poured to aqueous medium and stirred for 18 h at 80ºC. As
reference material a polymer without any lignin addition was synthesised according to
the same procedure (BPA.DA-St).
The prepared in this way polymers possessed form of porous microspheres.
Such materials can be potentially used as polymeric adsorbents for chromatographic
purposes or as precursors for carbonisation and production of porous carbon sorbents.
Thermal properties of the prepared microspheres were studied using TG-DTG-
DSC analyser. Measurements were carried out in helium atmosphere in the range of 50-
800ºC, at heating rate 10ºC/min. The obtained results are shown in Figure 2 in form of
TG and DTG plots.
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University of Coimbra, DEQ & DCV
100 200 300 400 500 600 700 800Temperature /oC
-16
-12
-8
-4
0
DT
G /
(%/m
in)
BPA.DA-St
BPA.DA-St-L
BPA.DA-St-LA
BPA.DA-St-LEA
Figure 2: TG (left) and DTG (right) plots of the presented polymers.
Initial decomposition temperatures (IDT) evaluated on the basis of TG results differ for
the studied materials, depending on the lignin component incorporated to the polymer
structure. Addition of unmodified lignin slightly increase value of IDT of BPA.DA-St-L
(260ºC) in comparison to BPA.DA-St (250ºC). In contrary, addition of lignin after
chemical modification causes decrease of initial decomposition temperatures of the
polymers. This effect is particularly well visible in case of the BPA.DA-St-LEA, that
starts to gradually decompose at about 150ºC. Under heating LEA easily loses its
numerous functional groups, therefore it is less thermally stable.
Thermal decomposition process for all the studied materials proceeds in almost
the same range of temperatures 325-535ºC. The greatest values of decomposition rate
(18%/min) and weigh loss (83%) were obtained for the polymer with no lignin
component. Introduction of L, LA or LEA to the polymeric structure resulted in the
decrease of the decomposition rates. Their values were 17, 15 and 9 %/min,
respectively. Similar tendency was observed for values of weight loss (81, 70 and 63%).
It means the lignin component (especially L and LA) slow down thermal destruction of
the BPA.DA-St.
Worth of noticing is also the fact, that amounts of chars obtained as residue at
800ºC after thermal analysis experiments increased from 8.5% for BPA.DA-St to 17.5%
for BPA.DA-St-LEA. It means the polymers containing lignin additives can be
considered as a potential precursors for carbonisation processes.
References
Myglovets, M., Poddubnaya, O.I., Sevastyanova, O., Lindström, M.E., Gawdzik, B.,
Sobiesiak, M., Tsyba, M. M., Puziy, A.M., (2014) Preparation of Carbon
Adsorbents from Technical Lignins by Phosphoric Acid Activation. Proceedings
of 5th NWBC, March 25th-27th, 2014, Stockholm, Sweden.
100 200 300 400 500 600 700 800Temperature /oC
0
20
40
60
80
100
Tg /%
BPA.DA-St
BPA.DA-St-L
BPA.DA-St-LA
BPA.DA-St-LEA
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University of Coimbra, DEQ & DCV
Xylan-cellulose films: improvement of hydrophobicity, thermal and
mechanical properties
Oihana Gordobil, Itziar Egües, Jalel Labidi
CHEMICAL AND ENVIRONMENTAL ENGINEERING DEPARTMENT, UNIVERSITY OF
THE BASQUE COUNTRY, PLAZA EUROPA, 1, 20018, DONOSTIA-SAN SEBASTIÁN,
SPAIN. [email protected]
Xylan-rich hemicellulose from corn cob agricultural waste has been used for new
material elaboration. Cellulose was used as reinforcement in different percentages to
improve performance of the films. Two types of composites were elaborated by solvent
casting. Hydrophilic films, composed by bleached hemicellulose (BH), cellulose and
glycerol as plasticizer, and hydrophobic films formed by acetylated bleached
hemicellulose (BAH) and acetylated cellulose as reinforcement. Hemicellulose was
acetylated in order to obtain a hydrophobic matrix and cellulose used as reinforcement
was also acetylated to improve compatibility between the two components. Obtained
hemicellulose was composed mainly by xylose (53%) and galacturonic (36%) and
showed a Mw 54000. FTIR spectra confirmed that the acetylation reaction was
successful in both cases. X-ray results indicated that the original structure of cellulose
was maintained and the fibers still have a reinforcement potential after treatment
(Tingaut et al. (2010). Acetylation process generated greater thermal stability of the
hemicellulose and cellulose. The initial degradation temperature (T5%) of BAH was
334ºC while BH began to degrade at 239ºC (Tingaut et al. (2010), Cang Sun et al
(1999)). For unmodified cellulose was 212°C and acetylated cellulose showed an initial
degradation temperature at 305ºC. Similar results were obtained by other authors after
modification treatments (Grace et al (2012), Urruzola et al (2013)). A significant
improvement was also observed in the thermal behaviour of the hydrophobic films
(Tmax~368ºC) respect to hydrophilic films (Tmax~300ºC). Fig. 1 shows that the
hemicellulose acetylation significantly enhances the hydrophobic character of the
obtained films. The film formed by bleached hemicellulose and glycerol (CBH) showed
a contact angle around 57º while the film elaborated with acetylated hemicellulose
(CBAH) was 72º. The Young’s modulus, tensile strain at break and tensile strength at
break of the biocomposites are shown in the Table 1. The results of mechanical
properties demonstrated that the films obtained from bleached hemicellulose had poor
properties. The addition of cellulose improved the mechanical properties, however at
higher concentration the properties decreased; the same behaviour was reported by
Zhang et al. (2008). Moreover, the acetylation of bleached hemicellulose generated
films with better mechanical properties, which were also improved by reinforcing with
acetylated cellulose. Similar behaviours had been found in literature when material was
reinforced with acetylated cellulose (Lin et al (2011).
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University of Coimbra, DEQ & DCV
Figure 1: Contact angle of composites.
Table 1: Average Values of Tensile strength at Break, Strain at Break and Young’s Modulus for
Composite Films in Tensile Testing.
References
Cang Sun, R., Fang, J.M., Tomkinson, J., Jones, G.L. (1999). Acetylation of wheat
straw hemicelluloses in N,N-dimethylacetamide:LiCl solvent system. Industrial
Crops and Products, 10, 209–218.
Grace, N., Fundador, V., Enomoto-Rogers, Y., Takemura, A., Iwata, T. (2012).
Syntheses and characterization of xylan esters. Polymer, 53, 3885-3893.
Lin, N., Huang, J., Chang, P.R., Feng, J., Yu, J. (2011). Surface acetylation of cellulose
nanocrystal and its reinforcing function in poly(lactic acid). Carbohydrate
Polymers 83 1834–1842. Tingaut, P., Zimmermann, T., Lopez-Suevos, F. (2010). Synthesis and Characterization
of Bionanocomposites with Tunable Properties from Poly(lactic acid) and
Acetylated Microfibrillated Cellulose. Biomacromolecules, 11, 454–464.
Urruzola, I., Serrano, L., Llano-Ponte, R., Ángeles de Andrés, Ma., Labidi, J. (2013).
Obtaining of eucalyptus microfibrils for adsorption of aromatic compounds in
aqueous solution. Chemical Engineering Journal, 229, 42–49.
Zhang, W., Zhang, X., Liang, M., Lu, C. (2008). Mechanochemical preparation of
surface-acetylated cellulose powder to enhance mechanical properties of
cellulose-filler-reinforced NR vulcanizates. Composites Science and Technology,
68, 2479–2484.
0
20
40
60
80
0 1 5 10 20 Co
nta
ct
angl
e θ
Cellulose %
Bleached hemicellulose and unmodified cellulose
Acetylated hemicellulose and acetylated cellulose
Hydrophilic films Hydrophobic films
Bleached hemicellulose + cellulose Acetylated hemicellulose + acetylated cellulose
Tensile
strength
(MPa)
Tensile
strain
(%)
Young’s
modulus
(MPa)
Tensile
strength
(MPa)
Tensile
strain
(%)
Young’s
modulus
(MPa)
Cel
lulo
se
con
ten
t %
0 3.3 ± 0.4 5.3 ± 1.7 3.3±0.9 44.1 ± 2.9 5.7 ± 2.1 2258 ± 207
1 4.8 ± 0.4 19.7 ± 3.2 146.5±28.7 48.5 ± 4.3 3.5 ± 1.0 2824 ± 228
5 5.8 ± 0.8 12.2 ± 4.9 206.3±2.5 51.0 ± 1.9 2.9 ± 0.8 3248 ± 408
10 7.5 ± 1.2 12.4 ± 3.8 170.2±11.8 -------- -------- --------
20 4.5 ± 0.3 12.6 ± 1.4 90.3±20.9 -------- -------- --------
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Microfibril angles of softwood and hardwood pulp fibres
Sabine Heinemanna, Elias Retulainen
b
VTT Technical Research Centre of Finland, Espoo/Finland
a
VTT Technical Research Centre of Finland, Jyväskylä/Finlandb
The microfibril angle (MFA) is an ultrastructural parameter to characterise wood cell
walls. The microfibril angle (MFA) affects axial strength properties of a fibre: strength
is increased but elongation decreased with decreasing angle. The final fibre wall
structure depends also on stock preparation processes such as refining, and on processes
to form a fibre network (Retulainen et al. 1998). The fibre wall thickness has been
observed to be negatively correlated with MFA (Koch 1972).
MFA analysis has been widely applied to several research questions using different
assessment methods depending on whether the fibres were investigated within the wood
matrix, or after they have been deliberated from the wood matrix in different pulping
processes. A comprehensive review of suitable methods was published some years ago
(Donaldson 2008). Microscope-based methods using polarisation techniques both for
transmitted light microscopes (Chun Ye et al. 1994, Chun Ye 2006 and 2006a,
McMillin 1973, Palviainen et al. 2004), and for confocal laser scanning microscopes
(Bergander et al. 2002, Jang 1998, Jang et al. 2002, Donaldson and Frankland 2004,
Vainio et al. 2007) have been used to determine MFA either from macerated wood
fibres, or from pulps fibres, basically with softwood origin. Most of the methods require
specifically equipped microscopes.
Within the ongoing EU project “Powerbond”, the study of single fibre mechanics is one
of the research targets. The general relationship between the stress-strain behaviour and
MFA of fibres is a well-known fact (Page and El-Hosseiny 1983), but little is known
about variations within a single fibre or the effect of refining. Therefore, a simple
method to determine MFA of selected single fibres is required. Polarimetry with a
transmitted light microscope was applied on earlywood, latewood, and compression
wood fibres from Norway spruce and Scots pine. Both reference pulps and refined pulps
were considered. Hardwood fibres from eucalyptus pulp that have not yet been
investigated to a larger extent were also measured. The MFA is determined from the
light intensity peak of fibres between crossed Nichols that are turned gradually within
the specimen plane, perpendicularly to the light beam, by 180° (Fig. 1). For intensity
evaluation, the ZEN software by Zeiss was used providing very small measuring spots.
Thus, fibre wall parts of special interest, e.g. areas close to damages, could be
investigated.
Resulting MFAs for different positions in the wall of the respective fibres will be
presented.
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University of Coimbra, DEQ & DCV
Figure 1: Softwood fibres between rotating crossed Nichols – Intensity changes of compression wood
(above), and latewood (below) depending on the position of the polarisation filters POL (polariser) and
ANA (analyser) - (numbers in the images POL/ANA). Left image shows the same fibres between non-
crossed polarisation filters.
References
Bergander, A., Brändström, J., Daniel, G., and Salmén L. (2002). Fibril angle variability in
earlywood of Norway spruce using soft rot cavities and polarization confocal
microscopy. J. Wood Sci 48, 255-263.
Chun Ye, Sundström, M.O., and Remes K. (1994). Microscopic transmission ellipsometry:
measurement of the fibril angle and the relative phase retardation of single, intact wood
pulp fibres. Applied Optics, 33(28), 6626-6637.
Chun Ye (2006). Measurement of the microfibril angle and path difference of intact pulp
fibers by spectroscopic imaging ellipsometry. Nordic Pulp Paper Res. J. 21, 520-526.
Chun Ye (2006a). Spectroscopic imaging ellipsometry: real-time measurement of single,
intact wood pulp fibers. Applied Optics 45(36), 9092-9104.
Donaldson, L. (2008). Microfibril angle: Measurement, variation and relationships – A
review. IAWA Journal 29(4), 345-386.
Donaldson, L., Frankland, A. (2004). Ultrastructure of iodine treated wood. Holzforschung
58, 219-225.
Jang, H.F. (1998). Measurement of fibril angle in wood fibres with polarization confocal
microscopy. Journal of Pulp and Paper Science 24(7), 224-230.
Jang, H.F., Weigel, G., Seth, R.S., and Wu, C.B. (2002). The effect of fibril angle on the
transverse collapse of papermaking fibres. Paperi ja Puu 84(2), 112-115.
Koch, P. (1972). The Raw Material. Agriculture Handbook No 420 Vol. 1, USDA-Forest
Service.
McMillin, Ch. (1973). Fibril angle of Loblolly pine wood as related to specific gravity,
growth rate, and distance from pith. Wood Science and Technology 7, 251-255.
Page, D.H. and El-Hosseiny, F. (1983) The mechanical properties of single wood pulp fibres.
Part VI. Fibril angle and the shape of the stress-strain curve. J. Pulp Paper Sci. 9(4),
TR99.
Palviainen, J., Silvennoinen, R., and Rouvinen, J. (2004). Analysis of microfibril angle of
wood fibers using laser microscope polarimetry. Opt. Eng. 43(1), 186-191.
Retulainen, E., Niskanen, K., and Nilsen, N. (1998). Fibers and bonds. Paper Physics,
Papermaking Science and Technology, Book 16, pp. 55-87. Fapet Oy, Jyväskylä.
Vainio, A., Sirviö, M., and Paulapuro, H. (2007). Observations on the microfibril angle of
Finnish papermaking fibres. 61th
Appita Annual Conference and Exhibition, Gold
Coast, Australia 6-9 May, 2007, proceedings 397-403
58
University of Coimbra, DEQ & DCV
MP-SPR: A new optical technique for characterization of cellulose
structure and kinetic interactions
Johana Kuncova-Kallioa, Niko Granqvist
b, Annika Jokinen
a, Janusz W. Sadowski
a
BioNavis Ltd, Ylöjärvi, Finland
a
University of Helsinki, Faculty of Pharmacyb
Cellulose receives attention as one of the nanomaterials of the future. It is the most
abundant polymer in the nature, low cost, ecological. It is envisioned as a future
material for food additives, drug delivery, implants, composites, paints, organic solar
cells, biofuel, printed electronics, biosensors,... Cellulose can be used in different
applications only by carefully selecting a favourable characteristics of the material. The
nanomaterial properties are driven by its micro- and nanoscopic features, such as
structure, shape, strength, and most importantly surface properties. The surface drives
the interface characteristics and by that the nature of the interactions, ability to self-
assemble or to remain chemically inert. Hence, with the shift from bulk cellulose to
more sophisticated applications and products, it is necessary also to introduce new
methods for characterization of the surface layers. In this paper, we present a novel
optical technique that can be used for characterization of cellulose structure and
interactions with it.
Surface plasmon resonance (SPR) is used for more than 20 years in drug discovery (De
Crescenzo 2008), selecting suitable drug candidates based on their binding properties.
Unfortunately, in its traditional configuration, it is not suited for measurements with
cellulose as it is limited to samples of less than 150 nm thick and provides only
measurements of relative changes of kinetic properties. A new optical configuration of
SPR, the Multi-Parametric Surface Plasmon Resonance (MP-SPR), enables use of
model cellulose thin films and gels of up to microns thick and provides absolute
measurements of kinetic properties as well as layer properties, such as swelling,
thickness or refractive index (Granqvist 2013).
MP-SPR method measures absolute amount of light reflected from the plasmonic
surface at a range of 40 degrees and at multiple wavelengths. Ultrathin layers of 5Å to
100 nm thickness (for all materials that can be deposited in this thickness) produce a
single SPR curve, thin layers of 300 nm to several microns (for optically transparent
materials only) typically produce multiple peaks in a SPR curve.
In the previous research, it was proven that it is possible to measure on model cellulose
surfaces. A protocol for spin-coating of model polymer surfaces, such as cellulose, on
SPR sensors has been published by (Liu 2011, Junka 2014, for instance). So far, the
MP-SPR method has been shown to be able to measure specific water uptake (Kontturi
2013), carbon dot attachment to cellulose nanofibrils (Junka 2014), or adsorption of
human immunoglobulin G (hIgG) and bovine serum albumin (BSA) to different
modifications of cellulose (Orelma 2011). There are several ongoing investigations in
the direction of cellulose for biofuel, regenerative medicine, drug delivery, organic solar
cells and printed electronics.
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University of Coimbra, DEQ & DCV
Meanwhile, with other materials, it was possible to show measurements of thickness
and refractive index on nanolayers made with CVD and ALD (Granqvist 2013),
dynamic structural changes of polymer (Malmström 2013), permeation of gases and
vapours into the polymer (Fig. 1), layer-by-layer antifouling material functionality
(Cado 2013). In the next stage, such measurements should be also applied to barrier
coatings on model cellulose surfaces. Furthermore, since MP-SPR has been shown to be
capable of measuring nanoparticle–living cell monolayer interactions and distinguish
between transcellular and paracellular pathways (Viitala 2013) for drug delivery, it can
be implicated that it could be used for nanotoxicity studies of different types of
cellulose nanoparticles and their surface modifications.
References
Cado, G., Aslam, R., Séon, L., Garnier, T., Fabre R., A. Parat, A. Chassepot, J.-C. Voegel, Senger, B.,
Schneider, F., Frère, Y., Jierry, L., Schaaf, P., Kerdjoudj, H., Metz-Boutigue, M.-H., Boulmedais,
F. (2013), Self-Defensive Biomaterial Coating Against Bacteria and Yeasts: Polysaccharide
Multilayer Film with Embedded Antimicrobial Peptide, Advanced Functional Materials, 23, 4801-
4809.
De Crescenzo, G., Boucher, C., Durocher, Y., Jolicoeur, M. (2008). Kinetic Characterization by Surface
Plasmon Resonance-Based Biosensors : Principle and Emerging Trends. Cellular and Molecular
Bioengineering, 1(4), p. 204-215.
Granqvist N., (2013). Characterizing Ultrathin and Thick Organic Layers by Surface Plasmon Resonance
Three-Wavelength and Waveguide Mode Analysis, Langmuir, 29 (27), 8561–8571. Junka, K., Guo, J., Filpponen, I., Laine, J., and Rojas, O.J (2014). Modification of Cellulose Nanofibrils
with Luminescent Carbon Dots. Biomacromolecules, 15, 876-881.
Kontturi, K.S., Kontturi, E., Laine, J. (2013), Specific water uptake of thin films from nanofibrillar
cellulose, J.Mater. Chem. A, 1, 13655-13663.
Liu, X., Vesterinen A-H., Genzer J., Seppälä, J.V., Rojas, O.J., (2011) Adsorption of PEO-PPO-PEO
Triblock Copolymers with End-Capped Cationic Chains of Poly(2-dimethylaminoethyl
methacrylate), Langmuir, 27(16), 9769–9780.
Malmström , J., Nieuwoudt, M.K., Strover, L.T., Hackett, A., Laita, O., Brimble, M.A., Williams, D.E.,
Travas-Sejdic, J. (2013). Grafting from Poly(3,4-ethylenedioxythiophene): A Simple Route to
Versatile Electrically Addressable Surfaces, Macromolecules, 46 (12), 4955–4965.
Orelma, H., Filpponen, I., Johansson, L-S., Laine, J., Rojas, O.J. (2011) Modification of cellulose films
by adsorption of CMC and chitosan for controlled attachment of biomolecules,
Biomacromolecules, 10. Viitala, T., Granqvist, N., Hallila, S., Yliperttula, M. (2013) Elucidating the Signal Responses of Multi-
Parametric Surface Plasmon Resonance Living Cell Sensing: A Comparison between Optical
Modeling and Drug–MDCKII Cell Interaction Measurements, PLoS ONE, 8(8): e72192
Figure 1: Permeation study with water, 50% and 100% ethanol (left). Model polymer surface is
spin-coated on top of one of the standard sensor slides, such as Au or SiO2 (right).
Ethanol permeated
to the polymer surface
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University of Coimbra, DEQ & DCV
Humidity response of thin films consisting of alternating layers of
amorphous and crystalline cellulose Elina Niinivaara, Eero Kontturi, Department of Forest Products Technology, School of
Chemical Technology, Aalto University, Finland The study of plant cell wall components in the 2-dimensional realm has become an area
of increasing interest among materials scientists. Thin films provide a suitable platform,
which allow for the investigation of the behaviour of polysaccharide matrices in varying
environments. The combination of the different cell wall polysaccharides in thin films
provides a way by which to study and possibly mimic their behaviour within the cell
wall.
Here, the controlled swelling of multilayer thin films of alternating amorphous and
crystalline cellulose layers was studied; the structure of which can be considered a
cellulose-based replica of the wood cell structure in which semicrystalline cellulose
microfibrils are surrounded by a matrix of amorphous lignin and hemicelluloses (Daniel
2007). The layers of amorphous cellulose were deposited in the form of trimethylsilyl
cellulose (TMSC) using the spin-coating technique. Upon regeneration with gaseous
hydrochloric acid, TMSC is known to convert into amorphous cellulose (Kontturi
2011). Cellulose nanocrystals (CNCs) on the other hand, were obtained through a
sulphuric acid treatment, which causes the degradation of the unordered region of
cellulose microfibrils, leaving the crystalline region intact (Rånby 1949).
Swelling of the thin film was carried out using ellipsometric porosimetry, with which
the relative humidity of the sample atmosphere can be accurately controlled. In the case
of thin films, swelling and deswelling as a result of an increase/decrease in moisture
content is restricted to 2-dimensional space. The CNC layer does not swell in the
presence of moisture however, the amorphous cellulose matrix does, imitating the
restricted swelling of the plant cell wall. Swelling of the films also causes an alteration
in the morphology of the cellulose layers; instead of defined layers, the CNC-network
becomes embedded into the amorphous cellulose.
Due to the restricted water uptake of the CNC-network, swelling of the thin film can be
controlled by the ratio of amorphous and crystalline cellulose, and as such, the
thickness, mass, water content, refractive index and electric conductivity can also be
controlled. This concept may provide an opportunity to use semicrystalline cellulose
thin films in smart materials.
References
Daniel, G. (2007) Wood and fiber morphology, in Ljungberg textbook: Pulp and paper
technology. Ek, M., Gellerdtedt, G., Henriksson, G. Eds. Fiber and polymer
technology, KTH, Sweden, Book 1, 49-71.
Kontturi, E., Suchy, M., Penttilä, P., Jean, B., Pirkkalainen, K., Torkkeli, M. and
Serimaa, R. (2011) Amorphous characteristics of an ultrathin cellulose film.
Biomacromolecules 12(39), 770-777.
Rånby, B.G. (1949) Aqueous colloidal solutions of cellulose micelles. Acta Chemica
Scandinavia 3, 649-650.
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Tuning the assembly of cellulose nanocrystals in 2D networks by
adjusting the chemical conditions in spin coating
Peyre Jessie, Kontturi Eero, Department of Forest Products Technology, School of
Chemical Technology, Aalto University.
Two dimensional structures represent a large spectrum of organization of matter
on thin surface such as islands, individual molecules or patterned structures. These
particular behaviors are interesting especially when one wants to create functional
materials as for example sensors, transistors, templates for nanomaterials…
Plant-based materials are known to create such 2D structures (Taajamaa 2011,
Taajamaa 2013) and our present work is focused on how these structures are created and
how to make them in a reproducible way. This study is based on nanocellulose treated
with a counter-ion exchange (Beck 2012), and purified in ethanol (Labet 2011) before
spin-coating on silica and mica wafer. To understand the mechanism of the 2D
structures we played with different parameters: nature of the counter-ion, concentration
of nanocellulose in solution (Figure 4), pH of the nanocellulose suspension (Figure 5)
and the nature of the wafers.
The understanding of this phenomenon has been obtained thanks to the use of
different technics of surface analysis: the Atomic Force Microscopy (AFM) to see the
influence of the different parameters on the formation of a 2D structure and the contact
angle measurements to know the surface energy of each material.
The results showed that the driving factor was the pH of the solution. The role
of the counter-ion is also relevant and lets us think that the forces involved in this
phenomenon are electrostatic forces more than the usual hydrophobic forces (Moriarty
2002, John 2010).
(a) (b)
Figure 4: Comparison of (a) H-cell and (b) Na-cell spin-coated on silica.
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(a) (b)
Figure 5: Influence of the concentration in NaOH: [NaOH]=(a) 0M and (b) 10-4
M
References
Taajamaa, L., Rojas, O.J., Laine, J. and Kontturi, E. (2011). Phase-specific pore growth
in ultrathin bicomponent films from cellulose-based polysaccharides. Soft Matter,
7, 10386-10394.
Taajamaa, L., Rojas, O.J., Laine, J., Yliniemi, K. and Kontturi, E. (2013). Protein-
assisted 2D assembly of gold nanoparticles on a polysaccharide surface. Chemical
Communications, 49,1318-1320.
Beck, S., Bouchard, J. and Berry, R. (2012). Dispersibility in Water of Dried
Nanocrystalline Cellulose, Biomacromolecules, 13, 1486-1494.
Labet, M. and Thielemans, W. (2011). Improving the reproducibility of chemical
reactions on the surface of cellulose nanocrystals: ROP of ε-caprolactone as a case
study. Cellulose, 18, 607-617.
Moriarty, P. and Taylor, M. D. R. (2002). Nanostructured cellular work. Physical
Review Letters, 89(24), 248303-1 – 248303-4.
John, N.S., Raina, G., Sharma, A. and Kulkarni, G.U. (2010). Cellular network
formation of hydrophobic alkanethiol capped gold nanoparticles on mica surface
mediated by water islands. Journal of Physical Chemistry, 133, 094704-1 –
09704-7.
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Synthesis and copolymerization of new acrylate derivatives of lignin
B. Gawdzika, B. Podkościelna,
a M. Sobiesiak
a, O. Sevastyanova
b
aDEPARTMENT OF POLYMER CHEMISTRY, FACULTY OF CHEMISTRY, MARIA
CURIE-SKŁODOWSKA UNIVERSITY, PL. M. CURIE-SKŁODOWSKIEJ 5, 20-031
LUBLIN, POLAND. bKTH, ROYAL INSTITUTE OF TECHNOLOGY, DEPARTMENT OF
FIBRE AND POLYMER TECHNOLOGY, DIVISION OF WOOD CHEMISTRY AND PULP
TECHNOLOGY, SE-10044 STOCKHOLM, SWEDEN
Lignin is one of the main components of the lignocellulosic material. Various technical
lignins are currently available in large quantities and viewed as a low value by-products
from the pulp and paper industry. However, structurally, lignin possesses properties
which make it a promising starting material for chemical modifications, leading to the
preparation of valuable polymeric materials with special properties. The reaction with
acrylic or methacrylic acid is one of the possible types of such modifications resulting
in the introduction of vinyl groups, capable for polymerization, into lignin structure.
This paper presents methods of the synthesis of lignin derivatives, which may find
application as a component in various types of polymerization. The novel method for
the synthesis of lignin containing microspheres for the solid phase extraction (SPE) was
evaluated.
L-O H +O
ClNaOH
L-O
O
L-O
O + COOH L- O
O H
O
O
L-O H + COOHL- O
O
a)
b)
O H
OCH 3
H
SH
O H
(or lignin)
lignin
LA
LE
LEA
Lignin acrylic acid
epichlorohydrinLignin
acrylic acid
I
II
L-OH =
Figure 1: Scheme of lignin modification.
Chemical modification of lignin
Scheme of lignin modification is presented in Figure 1. According to a first method,
modification of lignin directly with acrylic acid took place. The reaction of lignin with
acrylic acid in presence benzene, sulphuric acid and hydroquinone was carried out at
reflux temperature for 5 h. The obtained a modified lignin was washed and dried.
In the second method, modification lignin with epichlorohydrine and acrylic acid was
done, lignin was reacted with epichlorohydrine in presence propan-2-ol. Next, an
aqueous solution of NaOH was dropping out for 30 min. The lignin with epoxy groups,
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University of Coimbra, DEQ & DCV
was filtered off, washed and dried. Then, epoxy-lignin (LE) was placed together with
acrylic acid, triethylbenzylammonium chloride and hydroquinone and the whole content
was heated at 90-95oC for 5 h. The course of the modification of lignin was controlled
by elemental analysis and spectroscopic method (ATR) (Fig. 2).
2000 1600 1200 800Wavenumber cm-1
0.6
0.7
0.8
0.9
1
Tra
nsm
itan
ce
[%
]
L (Lignin)
LA
1720 cm-1
1175 cm-1
Figure 2: ATR spectra of lignin.
Synthesis of microspheres
For chromatography purposes particles of sorbents should possess uniform spherical
form. Such shape improves the efficiency of sorption process as it reduces a flow
resistance for mobile phase and minimizes the widening of chromatographic band
caused by diffusion.
Copolymerisation of styrene with divinylbenzene and lignin was performed in the
aqueous medium in suspension-emulsion procedure (Podkościelna et al. 2012). The
solutions containing DVB, St and a various amounts of lignin, the initiator (AIBN) and
the mixture of pore-forming diluents were added while stirring to aqueous medium. The
reaction mixture was stirred at 350 rpm for 18 h at 80oC.
Lignin was added to the monomers (St and DVB) before polymerization in three forms:
a) unmodified (0, 1, 3 and 6g), b) 3g of LA, c) 3g of LEA.
Thermal stabilities and degradation behaviours of the obtained microspheres were
studied by means of thermogravimetric (TG/DTG/DSC) analyses. Due to the presence
of the specific functional groups the obtained lignin-based microspheres have a
potential applications as a specific sorbent for the removal of phenolic pollutants from
water by SPE technique (Sobiesiak and Podkościelna 2010).
References
Podkościelna, B., Bartnicki, A., Gawdzik, B., (2012) New crosslinked hydrogels
derivatives of 2-hydroxyethyl methacrylate: Synthesis, modifications and
properties. Express Polym. Lett., 6(9), 759-771.
Sobiesiak, M., Podkościelna B., (2010) Preparation and characterization of porous DVB
copolymers and their applicability for adsorption (solid-phase extraction) of
phenol compounds. Appl. Surf. Sci. 257, 1222-1227.
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Nanopaper from almond shell
Eduardo Robles, Iñaki Urruzola, Luis Serrano, Jalel Labidi
Chemical and Environmental Engineering Department, University of the Basque Country, Plaza
Europa 1. 20018. Donostia-San Sebastián, Spain. [email protected]
The shell of common almond (Prunus dulcis) presents a considerable amount of
crystalline cellulose and thus it can be used as a source to obtain cellulose nanofibers.
Every year, around 0.8-1.7 million tons of almond shell are produced around the World
as by-product of the almond harvest (Pirayesh et al 2012).The isolation of cellulose
nanofibers from lignocellulosic feedstock requires, as a first step, the removal of lignin
using chemical treatments (Serrano et al. 2011). Nanopaper production is essentially
similar to the process used to produce regular (micro) paper; nanofibers are placed in
suspension to prepare a packed gel by filtering a previously prepared water suspension.
As water evaporates, capillary forces provide attraction between individual nanofibers,
thus forming the base of the nanopaper (Sehaqui et al. 2010). Nanopaper structures
show an interesting combination of elastic modulus, tensile strength and toughness
(Henriksson et al. 2008), thus making this an alternative material for multiple
applications, depending on the requirements of final use.
The purpose of this work is to compare mechanical properties from paper elaborated
with nanofibers from cellulose pulp obtained by two methods: organosolv process with
ethanol/water 60/40 v/v and alkali treatment with sodium hydroxide 7.5% w/w. After
delignification fibers were bleached with sodium chlorite and hydrogen peroxide. Then,
the different pulps were acetylated, hydrolyzed and homogenized to obtain cellulose
nanofibers. Nanopaper sheets from almond shell were produced and its properties were
compared to previously reported micropaper. The different treatments influenced the
crystallinity of the fibers which is related to the yield of cellulose nanofibers and
nanopapers as can be seen in Table 1. Relative density (ρ/ρc) for both methods was over
0.70, which is also related to mechanical properties as it is a function of the porosity of
the nanopaper.
Table 1: Main properties of micropaper
a (Yousefi et al 2013), and nanopapers from both methods.
Load
(N)
Tensile Stress
(MPa)
Strain
(%)
Modulus
(GPa)
Grammage
(g/m2)
Crystallinity
(%)
Micropapera - 9.5 1.5 2 78 69
Method 1 24.0 65.1 4.2 5.3 86 78.2
Method 2 24.2 62.7 2.9 5.6 94 79.8
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References
Henriksson M, Berglund LA, Isaksson P, Lindström T, Nishino T, Cellulose nanopaper
structures of high toughness, Biomacromolecules 9 (2008) 1579–1585.
Pirayesh, H., Khazaeian, A. (2012) Using almond (Prunus amygdalus L.) shell as a bio-
waste ability in Wood based composite, Composites: Part B 43 1475–1479.
Sehaqui H, Liu A, Zhou Q., Berglund L.A, Fast preparation procedure for large, flat
cellulose and cellulose/inorganic nanopaper structures, Biomacromolecules
11(2010) 2195–2198.
Serrano L, Urruzola I, Nemeth D, Belafi-Bako K, Labidi J, Modified cellulose
microfibrils as benzene adsorbent, Desalination 270 (2011) 143-150.
Yousefi H, Hejazi S, Mousavi M, Azusa Y, Heidari AH, Comparative study of paper
and nanopaper properties prepared from bacterial cellulose nanofibers and
fibers/ground cellulose nanofibers of canola straw, Industrial Crops and Products
43 (2013) 732– 737
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University of Coimbra, DEQ & DCV
Cellulose block copolymers
Reeta Salminen, Eero Kontturi,
Department of Forest Products Technology, School of Chemical Technology, Aalto University,
Finland
Cellulose modifications are significantly important in the research of new cellulose
based materials. When attaching polymers on cellulose, so far the emphasis has been on
grafting chains to and from the cellulose backbone. However, linear block copolymers
that include cellulose and a synthetic block in the backbone, have received relatively
little attention. Such block copolymers should possess interesting properties because of
the peculiar chemical nature of cellulose and could be utilized as binding material
between synthetic and biobased materials in composites. In this study, the synthesis of
cellulose-containing block copolymers was investigated along with their fundamental
phase separation properties on a 2D surface. Since cellulose is sparsely soluble,
cellulose acetate was chosen as the precursor for these copolymers, because of its
solubility in organic solvents.
The cellulose acetate block copolymers were synthetized by attaching an amino-ended
polystyrene homopolymer with reductive amination to the cellulose acetate reducing
end. The reducing end is present in polysaccharides due to mutarotation of the C-1 end
anhydroglucose unit. Mutarotation is present in aqueous solution and catalysed by the
presence of acid- or base-catalyst, but organic solvents mutarotation requires a catalyst.
Swain and Brown (1952) discovered that 2-hydroxypyranose (2-HP) catalyses
tertamethylglugose mutarotation in organic solvents and it is more effective than
dimolecular electrophile-nucleophile pair catalyst system. Using 2-HP not only enables
usage of non-watersoluble polysaccharides, such as cellulose acetate, but also might
decrease the reaction time of this otherwise slow reaction. This synthesis method could
even be applied for dissolved native cellulose instead of cellulose derivatives.
References
Swain, C.G., and Brown, J.F. (1952). Concerted Displacement Reactions. VIII.
Polyfunctional Catalysis. Journal of American Chemical Society, 74(10), 2538-
2543
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University of Coimbra, DEQ & DCV
Pulsed corona discharge oxidation in lignin modification Alexander Sokolov
a, Sergei Preis
a, Marjatta Louhi-Kultanen
a, Heiko Lange
b,
Claudia Crestini b
LUT Chemistry, Lappeenranta University of Technology
a
Dipartimento di Scienze e Tecnologie Chimiche, Universitá degli Studi di Roma ‘Tor Vergata‘b
Lignin is a potential raw material for various products including phenolic substances
and aromatic aldehydes (vanillin, syringaldehyde, vanillic acid, syringic acid) (Pinto, et
al. 2011). Traditional methods of lignin modification resulting in phenolic products
include oxidation with nitrobenzene, mild wet air oxidation and catalytic oxidation.
Drawbacks of these methods include severe toxicity problems with nitrocompounds,
strict safety requirements and thus high capital costs, and often poisoned costly
catalysts. The study considers the hypothesis that modification of lignin with pulsed
corona discharge (PCD) oxidation at ambient conditions may appear feasible and
beneficial method of lignin modification by its economic performance and
environmental safety. The PCD oxidation is the chemical free modification method and
has hydroxyl-radical and ozone as the main oxidation species effective in oxidation of
lignin. The influence of PCD treatment on phenolic and aliphatic OH groups and
changes in molecular weight were studied.
MATERIALS AND METHODS
Commercially available alkali
lignin (purchased from
Sigma-Aldrich) was used as a
test material. Figure 1 shows
the outline of the
experimental set-up. An
aqueous lignin solution was
circulated from the reservoir
tank through the reactor by
means of a pump. Solution is
spread between electrodes,
where the lignin aqueous
solution is treated with
oxidants. The experiments
were carried out at alkaline pH with different initial concentrations of lignin and the
composition of the gas phase – air and nitrogen-enriched air with the volumetric oxygen
concentration of 5 to 7% and 2 to 3%, respectively The studied parameters of pulsed
corona discharges include a voltage amplitude of 20 kV, a current of 400 A, for a
duration of 100 ns, giving the single pulse an energy of 0.3 J, at a pulse repetition
frequency of 840 pulses per second (pps). Lignin concentration was measured as tannic
acid in chromogenic reaction of the tannin/lignin method using the sodium carbonate
solution and Tanniver® solution (tannin-lignin reagent, HACH). Combined aldehyde
Pum p
System of
e lectrodesE lectric d ischarge
reactor
S torage tank
W ater
Voltage and current
m onitoring
Voltage pu lse
generator
Perforated p la te
N 2O 2
G as
cylinders
Input
ports
Sam ple feed
port
Figure 6: Experimental setup
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University of Coimbra, DEQ & DCV
concentration was determined by the colorimetric method developed by Evans (Evans et
al. 1973). 31
P nuclear magnetic resonance (31
P NMR) and gel permeation
chromatography (GPC) were implemented to clarify the influence of PCD treatment on
phenolic and aliphatic OH group contents and changes in molecular weight distributions
of the lignin sample, respectively.
RESULT AND CONCLUSIONS
An oxygen-thin atmosphere of 5-7 % or 2-3 % O2 provides less reactive oxidation
conditions, which are more favorable for aldehyde formation than air. On the other
hand, from the energy efficiency point of view, the PCD treatment at oxygen-thin
conditions consumes more energy compared to the treatment at air atmosphere (Figure
2). However, the tendency at low oxygen conditions gives an opportunity to reach the
higher energy efficiency by increasing the lignin concentration and finally exceed the
energy efficiency rate for the experiment in air atmosphere. GPC analyses shows that,
during the PCD oxidation, the major part of lignin decomposes to low molecular weight
fractions. Under milder oxidation conditions with lower oxygen content, an initial
depolymerization of lignin at the beginning of the PCD treatment is followed by a
subsequent polymerization of lignin fragments. According to 31
P NMR analyses of the
lignin after re-polymerization, the constitution in terms of the ratios between aliphatic
and aromatic end-groups, and in terms of the ratio of the different aromatic end-groups,
seems to be comparable.
References Evans, W.H. and Dennis, A. (1973) Spectrophotometric determination of low levels of
mono-, di- and triethylene glycols in surface waters. Analyst. 782-791.
Pinto Rodrigues, P.C., Borges da Silva, E.A., and Rodrigues, E. (2011). Insights into
oxidative conversion of lignin to high-added-value phenolic aldehydes. Ind. Eng.
Chem., 50, 741-748.
Figure 7: Yield (A) and energy efficiency (B) of aldehyde formation in different atmospheres with different initial lignin concentrations
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University of Coimbra, DEQ & DCV
Synergetic behaviour of clay and cellulose nanofibers on barrier
properties of nanocomposites
J. Trifola, D. Plackett
b, C. Sillard
c, J. Bras
c, O. Hassager
a, A. E. Daugaard
a, P.
Szaboa
DANISH POLYMER CENTRE, DEPARTMENT OF CHEMICAL AND BIOCHEMICAL
ENGINEERING, SØLTOFTS PLADS, BUILDING 227, DK – 2800, KGS. LYNGBY,
DENMARKa
FACULTY OF PHARMACEUTICAL SCIENCES, UNIVERSITY OF BRITISH COLUMBIA,
2405 WESBROOK MALL, VANCOUVER, BC V6T 1Z3, CANADAb
LGP2/GRENOBLE INP-PAGORA/CNRS, 461 RUE DE LA PAPETERIE, DOMAINE
UNIVERSITAIRE, C10065, 38402 SAINT MARTIN D’HÈRES CEDEX, FRANCEc
Poly (lactic acid) (PLA) has long been advocated as one of the best candidates for a
biobased material for food packaging. PLA has an inherently high permeability for
gases relevant to food packaging, such as oxygen and water vapour, and therefore the
barrier properties have to be improved in order to apply PLA in oxygen and/or water
vapour sensitive food packaging (Svagan et al. 2012).
In our research, nanocomposites with 1, 3 or 5 wt% of cellulose nanofibers, cellulose
whiskers or commercially available nanoclay (Cloisite™ 30B) were prepared and
evaluated for use in food packaging. Cellulose nanofillers were extracted from sisal
fibers using a recently developed chemical protocol ensuring high purity for either
cellulose nanofibers or cellulose nanocrystals. The cellulose nanofibers were obtained
from sisal fibers in a three-step procedure involving, first, a strong alkali treatment,
second, a bleaching process and finally an acetylation step. The cellulose whiskers were
prepared from the nanofibers by acid hydrolysis (Vargas et al. 2012).
The barrier properties for test materials were evaluated in oxygen permeability and
water vapour permeability tests on the three types of PLA composite film. Overall, it
was seen that the composites containing the nanocellulose fillers showed a substantially
lower permeability to oxygen than the nanoclay-based composites while both showed a
similar behaviour in terms of water barrier properties. This effect was even observed for
films with a similar degree of crystallinity, which indicates that this finding must result
from the properties of the filler rather than a crystallinity-related effect.
Moreover, the presence of more than one nanofiller (e.g., cellulose nanofibers and clay
or cellulose whiskers and clay) inside the polymeric matrix showed accumulative
behaviour in terms of barrier properties, providing for an important reduction in the
permeability of the PLA films, even at low nanofiller concentrations. We therefore
propose that such cellulose/clay hybrid nanocomposites could be promising materials
for future food packaging applications.
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References
Svagan, A. J., Åkesson, A., Cárdenas, M., Bulut, S., Knudsen, J. C., Risbo, J., &
Plackett, D. (2012). Transparent films based on PLA and montmorillonite with tunable
oxygen barrier properties. Biomacromolecules, 13(2), 397–405.
doi:10.1021/bm201438m
Vargas, G., Trifol, J., Algar, I., Arbelaiz, A., Mondragon, G., Fernandes, S. C. M.,
Mujika, F., Mondragon, I.(2012). Nanostructured composite materials reinforced with
nature-base.
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University of Coimbra, DEQ & DCV
Structural and chemistry analysis of barley endosperm by polarized
Raman spectroscopy (PRS).
L.Galvis
a, C.Bertinetto, T.Vuorinen
Aalto University, School of Chemical Technology, Espoo, Finland a
The chemical composition and microstructure of cereal kernels determine the outcome
of several food processing techniques such as milling, gelatinization and malting.
Optical microscopy is a standard procedure for histological section analysis of chemical
distribution inside kernels but requires the implementation of time-consuming staining
protocols.
Polarized Raman micro-spectroscopy (PRM) allows analysis of both chemical
composition and molecular orientation of cereal kernels materials without staining of
prepared sections. Moreover, high resolution maps (0.6-1 μm) of chemical bonds over
sections can be obtained.
In this work, barley kernels are mapped using PRM to evaluate both chemical and
structural changes upon malting. Due to band overlapping of carbohydrates and protein
over great part of the spectra range and the presence of embedding media signal on the
sections, a multivariate analysis that includes band-targeted entropy minimization
(BTEM) and basis analysis (BA) was used to resolve individual component spectra and
reconstruct images of the relative signal of each component. Resulting images of the
endosperm close to the aleurone layer in a malted kernel are shown on Figure 1. The
BTEM-resolved spectra are in accordance with the ones obtained from individual
compounds. Moreover this method could obtain information on the anisotropic response
of starch spectrum (shown in Figure 1E).
Figure 1: Reconstructed Raman images of the BTEM that coincide with the model compounds A)
β-glucan B) protein C) embedding media D) starch E) anisotropic component of starch. The Raman
mapping was performed at 0opolarization of laser.
Starch granules like the observed in Figure 1D are composed of concentric shells of
alternating semi-crystalline layers made mainly of amylopectin double helices, and
amorphous layers that are rich in amylose [1]. In order to evaluate the anisotropic
behaviour of the starch spectra at different polarization directions of the laser a variance
analysis was performed on individual starch granules. Most bands exhibit anisotropic
response but the highest corresponds to the band located at 865 cm-1
that is assigned to
the vs C-O-C/ breathing ring, as shown in Figure 2A. This observation suggests that the
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University of Coimbra, DEQ & DCV
C-O-C band at 865 cm-1
might be sensitive to the molecular orientation of the double-
helix amylopectin located in the semi-crystalline regions inside the starch granules [1].
Figure 2: A) Starch spectra on a granule area defined by the blue square on the sketch. The spectra
were taken at 0o and 90
o polarization of the laser. The higher anisotropic response is observed for
the Raman band located at 865 cm-1 assigned to Vs C-O-C/ring breathing. B) Raman image of the
band ratio 865 cm-1
/1343cm-1
at 90o polarization angle of the laser of a single granule.
Previous work on crystal structure of A-amylose showed that C-O-C groups in the
glucosyl ring appear roughly aligned along the double helix, suggesting that its global
Raman tensor has the largest polarizability along to the double helix [3]. In this sense,
the Raman image of a single granule shown on Figure 2B that corresponds to the ratio
of the bands 865 cm-1
/1343cm-1
seems to be in accordance with the standard model of
amylopectin organization in the semi-crystalline shells, in which the amylopectin fibres
are oriented in a radial fashion and originates higher intensity values of the C-O-C band
at 865 cm-1
when the polarization direction of the laser is parallel to the amylopectin
double helix.
Conclusions and outlook:
The BTEM technique allows spectral reconstruction and mapping of pure components
on kernel sections in accordance with model compounds spectra. Our next step is to
study the anisotropic response of the band at 865 cm-1
to evaluate the possibility of
developing amylopectin orientation maps on starch granules.
References
1. Wellner, N., Dominique, M.R., Parker, M.L., Highley, T.L. and Morris, V.J. (2011).
In situ Raman microscopy of starch granules structures in wild type and ae mutant
maize kernels. Starch, 63, 128-138.
2. Gebhardt, R., Hanfland, M., Mezouar, M., and Riekel, C. (2007). High-Pressure
Potato Starch Granule Gelatinization: Synchrotron Radiation Micro-
SAXS/WAXS Using a Diamond Anvil Cell. Biomacromolecules, 8 , 2092-2097.
3. Popov, D., Buléon, A., Burghammer, M., Chanzy, H., Montesanti N., H., Putaux, J.-
L., Potocki-Veronèse, G. and Riekel, C. (2009). Crystal structure of A-amylose :
A revisit from Synchrotron Microdiffraction Analysis of Single Crystals.
Macromolecules, 42, 1167-1174
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5. Useful information
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University of Coimbra, DEQ & DCV
How to reach Coimbra
Coimbra is located in the Center of Portugal, 40 km away from the cost. The city has a
population of 120.000 with about 35.000 students (this means a lot of noisy…) most of
them studying (or not) at the University of Coimbra. The University dates back to the
13th century (1290) and is the oldest university in Portugal and one of the oldest in
Europe. The old part of the university is one of the main Portuguese touristic
destinations.
The nearest main Portuguese airport from Coimbra is Oporto airport. There is a metro
connection (http://www.metrodoporto.pt/en/, purple line) from Oporto airport to
Oporto railway station (Campanhã). Buses or taxis are also available. At Campanhã
railway station there are several connections to Coimbra. There are two types of trains:
"Pendular" (blue ones in the time table) and "Intercidades" (green ones). Pendular trains
are faster but more expensive. The trip will take approximately 1h by Pendular and a
little more by Intercidades. The timetable is available at
http://www.cp.pt/StaticFiles/CP/Imagens/PDF/Passageiros/horarios/longo_curso/ap_ic.
pdf (at the “Sentido Norte-Lisboa” table).
Coimbra can also be easily reached flying to Lisbon airport. Take the metro or a taxi to
the “Lisboa Oriente” railway station. By metro it is the 3rd station after the airport. A
taxi will cost between 6 - 10€ (depending on hour and luggage). As in the case of
Oporto there are two types of trains connecting Lisboa to Coimbra: Pendular and
Intercidades. The trip takes approximately 1h45 by Pendular and 1h55 by Intercidades.
The timetable is available at
http://www.cp.pt/StaticFiles/CP/Imagens/PDF/Passageiros/horarios/longo_curso/ap_ic.
pdf (at the “Sentido Lisboa-Norte” table). You must leave the train at "Coimbra B”
railway station. If you go to Hotel D. Inês, Hotel Vila gale or Hotel Tivoli, the easier
way is to take a taxi. If you go to Hotel Astória or Hotel Ibis, instead of the taxi you
may use the train connecting Coimbra-B and Coimbra-A railway stations (no additional
ticket is necessary). From Coimbra-A railway station, which is in the city centre, the
two hotels are in a walking away distance.
Accomodation and Transport
The organization will provide a bus to transport participants from the hotels to the
Department of Chemical Engineering and the way back to the hotels. The suggested
hotels are the only ones served by the bus. Please, note that the prices are indicative.
Participants must book directly their rooms. Public transport (Buses 34 and 38) connect
City centre with the Campus II of the University.
For accommodation in Coimbra following hotels are suggested.
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Hotels Rates per room
per night
Breakfast Contact
Hotel Vila Galé Coimbra**** Single 65€
Double 79€
Suite 103€
Yes www.vilagale.pt
+ 351 217 907 619
Hotel Tivoli Coimbra**** Single 59€
Double 69€
Yes www.tivolihotels.com
+ 351 239 858 300
Hotel D. Inês Coimbra*** Single 51€
Double 61€
Yes http://www.hotel-dona-ines.pt
+ 351 239 855 800
Hotel Astória Coimbra*** Single 65€
Double 75€
Yes http://hotel-astoria-coimbra.h-rez.com
+ 351 217 991 930
Hotel Ibis** 45€ No (6€) www.ibishotel.com
+ 351 239 852 140
For more information about Coimbra hotels visit:
www.booking.com/Coimbra-Hoteis
www.turismodecoimbra.pt/en/ondeficar/hoteis.html
Meeting Venue
Department of Chemical Engineering – University of Coimbra
Polo II – Pinhal de Marrocos
URL: http://www.uc.pt/fctuc/deq/
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University of Coimbra, DEQ & DCV
Dinner (May 8)
The meeting dinner will be at Loggia restaurant
(https://ptpt.facebook.com/www.loggia.pt ), located at the Machado de Castro National
Museum (www.museumachadocastro.pt), just nearby the most important nucleus of the
University of Coimbra Unesco World Heritage: (http://worldheritage.uc.pt/)
Tourist Offices
- Posto de Informação Turística da Turismo do Centro de Portugal (Tourist centre)
Largo da Portagem
3000-337 Coimbra
Telephone: 239 488 120 ; Fax: 239 488 129
E-Mail: [email protected]; Web: www.turismodocentro.pt/coimbra
Schedule: 9am-6pm
Useful Contacts Emergency Number: 112 (first aid, police, fire services)
Hospital of the University of Coimbra
Telephone: (+351) 239400400 / (+351) 239827446
Taxis: Politáxis
Telephone: (+351) 239715445 / (+351) 239499090 / (+351) 239826622 / (+351)
239822287
Service for Foreigners and Borders
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University of Coimbra, DEQ & DCV
Telephone: (+351) 239853500 / (+351) 800204327 (free call)
Local Organizers:
Paulo Ferreira ([email protected]) (+351) 239798700 / 747
Jorge Canhoto ([email protected]) (+351) 239855210
The City
Coimbra is one of the most important urban centers of Portugal after the larger Lisbon
Metropolitan Area and Oporto Metropolitan Area. Coimbra plays a role as the chief
urban centre of the central part of the country.
With a dense urban grid, the city of Coimbra is famous by its monuments, churches,
libraries, museums, parks, nightlife, healthcare and shopping facilities, but above all for
its intense cultural life, centered on the University of Coimbra, one of the
oldest universities in Europe.
Culture
- Fado
Fado de Coimbra (Coimbra fado) is a highly stylized genre of fado (a Portuguese music
genre) born in the city of Coimbra. The music is usually linked to the Portuguese word
saudade which means to miss or to long for someone or something.
This fado is closely linked to the academic traditions of the University of Coimbra and
it is accompanied by a Portuguese guitar and a classical guitar; the tuning and sound of
the Portuguese guitar in Coimbra is quite different from that of Lisbon.
According to tradition, to applaud fado in Lisbon one would clap his hands, while in
Coimbra cough as if clearing the throat is the typical way.
- Student festivals
Coimbra is also known for its university students' festivals. Two are held every year and
the more important is Queima das Fitas (“The Burning of the Ribbons”). It takes place
at the end of the second semester (usually in the beginning of May) and it is one of the
biggest student parties in all Europe. Celebrating the end of graduation courses,
symbolized by the ritual burning of the ribbons representing each faculty of the
University of Coimbra, it lasts for 8 days, each for each faculty of Coimbra's University.
During this period, a series of concerts and performances are held, turning Coimbra in a
lively and vibrant city. It also includes a parade of the university students, sport
activities, gala ball, and many other public events and traditions, such as the historical
nighttime student fado serenade (Serenata Monumental) which happens in the stairs of
the Old Cathedral of Coimbra for a crowd of thousands of students, tourists and other
spectators.
The usage of academic dress for undergraduates, or traje academico is still widespread
and has even gained popularity in recent decades. The traje is composed of black
trousers (or skirt, for female students), white shirt, black tie, a black overcoat, known as
batina and a black robe. The outfit, originally created for the students of the University
of Coimbra, is a key part of the praxis symbolizing equality, respect and humility Reportedly, during Queima das Fitas, more beer is drank in one week than in the
Oktoberfest in Munich, Germany.
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University of Coimbra, DEQ & DCV
Places to Visit
The University
The University of Coimbra is one of the main Portuguese touristic destinations. Every
year the Paço das Escolas is visited by about 200 thousand tourists from all over the
world. The history of the University of Coimbra dates back to the century subsequent to
the very foundation of the Portuguese nation, since the University was established in the
13th
century, in 1290.
The Main University Area accommodates merely a small part of the whole which
constitutes the University of Coimbra today. In fact it occupies various areas in the city,
with its eight faculties, half a score research centres, an Institute for Interdisciplinary
Research, structures for the encouragement of entrepreneurship and of connection to the
management field, the University stadium and many other sport facilities, the Science
Museum, the Gil Vicente Academic Theatre, the Botanical Garden, structures of support
for students life (dormitories, university restaurants, bars, study areas, centres for social
contact) and the biggest academy in the country. In 2013 the University of Coimbra, the
uptown ("Alta") and Sofia were classified by UNESCO as World Heritage sites.
The Main University Area
In Portugal and a little around the rest of the world, the idea of the institution University
of Coimbra is closely connected to the Main University Area, a heterogeneous
architectural ensemble where the constructions of the so-called New State are put in
relief, especially the Pateo and the Paço das Escolas looked down upon by the famous
University Tower. With the intent to honour the entrance into the court of the
University, the Porta Férrea is the first important work undertaken by the School after
acquiring the building thus idealized as a triumphal arch with a double façade. The Via
Latina, erected during the second half of the 18th century, constitutes in its essence, a
skilful solution to facilitate the access between the vice-rector's court, the Sala dos
Capelos and the Main Areas.
The Sala dos Capelos is the most important room of the University of Coimbra. In this
space there is the celebration the public probes of PhD and aggregation as also the most
important ceremonies of the academic life. When visiting the Sala dos Capelos, you
may also visit the Private Examination Room and the Arms Room. The Private
Examination Room was an integrating part of the royal wing of the palace. It was a
royal chamber, that is, the place where the monarch stayed overnight. The Arms Room
was part of the royal wing of the old palace. It accommodates a full array of arms
(halberds) of the Academic Royal Guard, which are still used today by the Halberdiers
(guards) in the formal academic ceremonies (solemn “honoris causa” doctorates, the
rector's investiture, formal beginning of the classes).
The Biblioteca Joanina (“Joanine Library”) is one of the most notable and renowned
libraries in Portugal. Its construction is dated between 1717 and 1728 and its first books
were received after 1750, being that it houses an excess of 200,000 volumes from the
16th
, 17th
and 18th
centuries. Hundreds of people come from all over the world to
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University of Coimbra, DEQ & DCV
marveling the painted ceilings, the gilded carved wood and the precious wood of the
tables.
In the Paço das Escolas one can also visit the Saint Michael’s Chapel. It was built in
the beginning of the 16th
century, replacing another chapel, probably from the
12th
century. Its architectural structure is Manueline with a visibly decorative style,
especially in the huge windows of the main nave and in the transept arch.
Monuments and Museums
In the center of the Old University there is the Science Museum, awarded with the
international Micheletti Prize for museums in 2008. It is an interactive space based on
the University’s collections of scientific instruments and on experiments and activities.
(Tues.- Sun.: 10 a.m. - 6 p.m.; Closed Mon; Adults - € 3 ; Bus: 1A, 1F, 34, 103)
Also in the University, there is the Machado de Castro National Museum. The
museum’s name pays homage to one of the greatest Portuguese sculptors, Joaquim
Machado de Castro (1731-1822), who was born near Coimbra and was sculptor to the
royal house in the reigns of José I, Maria I and João VI. (Tues. - Sun.: 10 a.m. - 6 p.m.;
Closed Mon.; € 4; Bus: 1A, 1F, 34, 103)
Near the river, situated in the Dr. Manuel Braga Park, there is the Water Museum,
housed in a former water collection plant dating from 1922. (Tues. - Sun.: 10 a.m.- 1
p.m./ 2 – 6 p.m; Closed Mon.; Free entry; Bus: 10, 11T, 24T, 33, 41)
Besides this, you can see the Almedina Tower and Almedina Arch, the Convent of
Santa Clara-a-Nova, Santa Cruz Church, the patio of the Inquisition, Old Cathedral,
among many others.
Gardens/Nature
Penedo da Saudade is located in the top hills of Coimbra. In the 20th century, during
course reunions & other student occasions, it became the custom to fix here a stone
plaque with commemorative verses. (Bus:4)
In the Old University there is the Botanic Garden. Its exuberant vegetation reflects
botanical studies and contacts with the four corners of the earth. (Garden: Mon-Fri:
9am-5.30pm – free admission; Greenhouses:Mon-Fri: 9am-12.30pm/2.30pm-5pm - €2 ;
Bus: 1A, 11, 24)
To a romantic visit you can go to Quinta das Lágrimas Gardens, named to the ill-
starred love between the lady-in-waiting Inês de Castro and Prince Pedro. The romantic
tragedy makes this the scene of Inês death. (Tues.-Sun.:10am-7pm; €2; Bus 18)
In order to relax there is a large green space with bars, restaurants and the Central
Portugal Pavillion, in the Mondego Green Park, situated by the river.
Shopping
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University of Coimbra, DEQ & DCV
The medieval center of Coimbra is unusual in retaining a number of independent
bookshops, boutiques, toyshops, galleries, antique and food shops. There are several
bookstores, cafes, restaurants and esplanades. The most important shopping malls are
Coimbra Shopping, Dolce Vita (located in the city center) and Forum Coimbra (in
the other bank of the river). Shops are open on weekdays from 9 a.m. to 1 p.m and from
3 p.m. to 7 p.m.; some shops are also open at lunch-time and Saturday morning. In
shopping centres the schedule is longer - from 10 a.m. to 11 p.m/midnight. For public
services, times are Monday to Friday, 9 a.m. to 12.30 p.m. and 2 to 5.30 p.m. Banks are
open from 8.30 a.m. to 3 p.m.
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University of Coimbra, DEQ & DCV
6. Participants
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University of Coimbra, DEQ & DCV
Alexander Sokolov [email protected]
Alvaro Tejado [email protected]
Ana Lourenço [email protected]
Baeta Podkościelna [email protected]
Barbara Gawdzik [email protected]
Claudia Crestini [email protected]
Cristina Marques [email protected]
Daniel Geoffrey [email protected]
Delphine Ménard [email protected]
Dimitris Argyropoulos [email protected]
Dinesh Fernando [email protected]
Dominika Janiszewska [email protected]
Edouard Pesquet [email protected]
Eduardo Robles [email protected]
Elina Niinivaara [email protected]
Fabian Herz [email protected]
Fabiola Vilaseca [email protected]
Gary Chinga Carrasco [email protected]
Grzegorz Kowalk [email protected]
Guy Costa [email protected]
Harald Grossman [email protected]
Humbert DelliColli [email protected]
Iñaki Urruzola [email protected]
Ivo Valchev [email protected]
Jessie Peyre [email protected]
João Martins [email protected]
Johana Kuncova-Kallio [email protected]
Johannes Leitner [email protected]
Jokin Hidalgo [email protected]
Jon Trifol [email protected]
Jorge Canhoto [email protected]
Jose Alberto Mendez [email protected]
José Ataíde [email protected]
José Gamelas [email protected]
Kourosh Latifi [email protected]
Leonardo Rojas [email protected]
Manuel Mikczinski [email protected]
Nikolay Yavorov http://www.uctm.edu/index_en.html
Oihana Gordobil [email protected]
Paavo Penttila [email protected]
Pasi Kallio [email protected]
Paulo Ferreira [email protected]
Paulo Mendes de Sousa [email protected]
Philip Turner [email protected]
Primoz Oven [email protected]
Raphael Passas [email protected]
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University of Coimbra, DEQ & DCV
Reeta Salminen [email protected]
Ritva Serimaa [email protected]
Sabine Heinemann [email protected]
Sara Rodrigues [email protected]
Sedat Ondaral [email protected]
Sheetal Gangula [email protected]
Stefania Angelini [email protected]
Tom Lindström [email protected]
Tomas Larsson [email protected]
Vasiliki Gkountsidou-Iakovou [email protected]
Veronique Aguie [email protected]
Wolfgang Bauer [email protected]
Yan Pereira [email protected]
Zurine Hernandez [email protected]
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7. Notes
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University of Coimbra, DEQ & DCV
88
University of Coimbra, DEQ & DCV
89
University of Coimbra, DEQ & DCV
I went to the country with big plans.
But all I found was grass and trees…
Álvaro de Campos