University of Coimbra, DEQ & DCV/media/documents/sebe/cost-action/events/work… · University of...

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University of Coimbra, DEQ & DCV

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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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The organizers acknowledge the support of the

following institutions:

Banco Bilbao Viscaya Argentaria (BBVA)

Caixa Geral de Depósitos (CGD)

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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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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.

http://www.cost.eu/service/glossary/Action

http://www.cost.eu/domains_actions/fps/Actions/service/glossary/Action

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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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1. Agenda

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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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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


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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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


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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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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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.

mailto:[email protected]

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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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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.

25


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.

26


3. Short presentations

27


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.

28


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.

29


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.

30


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.

31


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.

32


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

33


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.

34


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

35


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

36


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.

37


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.

38


4. Posters

39


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.

http://www.unilim.fr/glycophy

http://www.unilim.fr/glycophy

40


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,

41


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).

42


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


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


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.

45


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.

46


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


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


48


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


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.

50


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


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


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.

53


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

54


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).


55


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 -------- -------- --------

56


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.

57


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


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.

59


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

60


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.

61


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.

62


(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.

63


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,

64


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.

65


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


66


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

67


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

68


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

69


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

70


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.

71


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.

72


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

73


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

74


5. Useful information

75


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.

http://www.cp.pt/StaticFiles/CP/Imagens/PDF/Passageiros/horarios/longo_curso/ap_ic

http://www.cp.pt/StaticFiles/CP/Imagens/PDF/Passageiros/horarios/longo_curso/ap_ic

76


Hotels Rates per room

per night

Breakfast Contact

Hotel Vila Galé Coimbra**** Single 65€

Double 79€

Suite 103€

Yes www.vilagale.pt

[email protected]

+ 351 217 907 619

Hotel Tivoli Coimbra**** Single 59€

Double 69€

Yes www.tivolihotels.com

[email protected]

+ 351 239 858 300

Hotel D. Inês Coimbra*** Single 51€

Double 61€

Yes http://www.hotel-dona-ines.pt

[email protected]

+ 351 239 855 800

Hotel Astória Coimbra*** Single 65€

Double 75€

Yes http://hotel-astoria-coimbra.h-rez.com

[email protected]

+ 351 217 991 930

Hotel Ibis** 45€ No (6€) www.ibishotel.com

[email protected]

+ 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/

http://www.vilagale.pt/


http://www.tivolihotels.com/


http://www.hotel-dona-ines.pt/


http://hotel-astoria-coimbra.h-rez.com/


http://www.ibishotel.com/


http://www.booking.com/Coimbra-Hoteis

http://www.turismodecoimbra.pt/en/ondeficar/hoteis.html

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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

http://worldheritage.uc.pt/

78


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.



79


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

80


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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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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6. Participants

83


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]






































http://www.uctm.edu/index_en.html









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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

86


87


88


89


I went to the country with big plans.

But all I found was grass and trees…

Álvaro de Campos

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