Joint ILL ESRF Workshop
“Chemical Engineering and Mechanics in Wood:
X-ray and neutron scattering, microscopy and modelling”
23-24 March 2017
Institut Laue Langevin, Grenoble, France
Abstract Booklet
2
Introduction
Wood swelling and related mechanical property variations are crucial problems for the durability and
usage in construction and furniture and for the preservation of cultural heritage. There are several
established methods for wood impregnation and chemical modification but none of them can be
predictively modeled. A robust and comprehensive microstructural characterization preliminary to the
modelling is based on combined real and indirect space studies. This joint ILL and ESRF workshop will
present experimental possibilities to follow adsorption of water, salts or reactives in cellulose-based
materials (techniques, sample-environments: humidity, temperature, pressure, mechanical stress) in
link with open questions from theoreticians (success and failure of predictive models) to current
limitations in commercial applications (process, properties enhancement, preservation).
Keywords / Thema:
- Microstructure and thermodynamics of wood and wood products
- Processes for increasing durability via controlled swelling
- Mechanical-chemical processes and properties
Local Organizing committee
M. Capron (ESRF, Grenoble), B. Demé (ILL, Grenoble), J.-C. Gabriel (CEA, Grenoble), I. Grillo (ILL,
Grenoble), T. Grünewald (ESRF, Grenoble), S. Prévost (ILL, Grenoble), T. Zemb (ICSM, Bagnols sur Cèze)
Conference secretary
A. Mader
Contact : [email protected]
3
PROGRAMME
23 March 2017
Session 1
8:45 -9:00 Opening
9:00 -9:40
T. Zemb,
4
The Micro-and Nanoscale structure of heat steam compressed wood
5
Non-specific tracking of transport pathways in the nanostructure of
wood by ultra-small nanoparticles using electron microscopy, X-ray
scattering, and confocal Raman imaging
Coffee break
Wood abnormal swelling in mixed solvents and influence on
mechanical properties. Towards a better understanding of the
molecular interactions between wood macromolecules and organic
liquids?
6
8
P. Pentillä
Resolving small-angle neutron scattering data to understand the
nanoscale structure of wood
9
J.F. Gonzales
Waterborne wood finishes: influence of the ambient humidity on
their water content and viscoelastic properties
H. Rennhofer
10:05 -10:30 Oral 2
J. Segmehl
10:30 -10:45
session 2
Invited
F. di Renzo
contribution
11:25-11:40 Oral 3
11:40 -12:00 Oral 4
Page
Conservation of archeological wood: the Vasa and Oseberg case
studies
Invited
P. Baglioni
contribution
9:40 -10:05 Oral 1
10:45 -11:25
ICSM deputy director, Marcoule, France
12:00 -13:45
13:45 –
14:00
Session 3
Lunch
M. Johnson, J.
ILL –ESRF, the director’s word
Susini
X-ray scattering as a versatile tool to image cellular structures :
ESRF
M. Capron, T.
14:00 -14:35
Possibilities and applications at the ESRF
contribution Grünewald
7
14:35 -15:00
ILL
B. Demé
contribution
15:00 -15:25
ICSM
R. Podor-J.
Contribution Lautru
BerILL the new high-precision chamber for in situ control of
temperature and humidity
11
Environmental microscopy under humidity control
12
G. Chaumat
Development of a new conservation treatment of wood for outdoor
applications
13
15:25 -15:50 Oral 5
E. Piva
Neutron imaging PEG-treated archaeological wood from the Mary
Rose: the role of a hydrogel on a degraded cellular structure
14
15:50 -16:15 Oral 6
16 :15 -17:30
Invited
17:30 -18:10
W. Kunz
contribution
Session 4
10
18:10 -18:35
J. Berg
18:35 -19:00 Oral 8
G. Chaumat
19:45
Coffee break and discussion
Cellulose/chitin and lignin/chitin hybrid materials
15
Oriented crystallization of barium sulfate confined in native wood
structures: a high-resolution study via scanning wide-angle X-ray
scattering
16
Acidification of treated composite archaeological artifacts
17
Workshop dinner Fantin LaTour
4
24 March 2017
Session 5
Invited
8:30 -9:10
contribution
9:10 -9:35 Oral 9
9:35 -10:00 Oral 10
10:00 10:25
Oral 11
L. Bertinetti
18
Identification of lignin yield stress in the wood cell wall by a
19
combination of micropillar compression, WAXD, wet chemical analysis
J. Schwierdzyk
and micromechanical modeling
Structural analysis and dynamics properties of archaeological wood
with high-resolution solid-state 13C NMR
21
M. Bardet
22
J. Sandak
Mechanical stresses and moisture changes in wood assessed at
molecular level with near infrared spectroscopy
10:25 10:30
session 6
An equation of state approach to describe water sorption, swelling
and passive actuation of secondary cell walls
Coffee break
Advances in cellulose dissolution: From scattering and rheology to a
B. Medronho new NMR approach
23
10:40 11:20
Invited
contribution
11:20 11:45
Oral 12
Heterogeneous swelling and dissolution of cellulosic fibers in aqueous 24
N. Le Moigne solvents: role of cell walls and supramolecular structure
11:45 12:10
Oral 13
D. Derome
Absorption in wood : capturing all the effects by MD
25
12:10 12:35
High-resolution structure of cellulose to the nanostructureof wood:
Y. Nishiyama neutron / X-ray scattering and molecular modeling
26
Oral 14
27
Oral 15
Development of a new characterization method to analyse
S. Tapin-Linga cypermethrin penetration in wood material by immunolabelling
12:35 12:50
12:50 13:00
Conclusion ... then lunch
5
SESSION 1
Conservation of archeological wood: the Vasa and Oseberg case studies
Content
P. Baglioni1
1
Florence University, Dipartimento di Chimica, 50019 Sesto Fiorentino, Firenze, Italy
The conservation of the Swedish Vasa and the Norvegian Oseberg shipwrecks is a challenge due the
unique history of its recovery and the interventions made for their wood preservation. Among the
main wood components, hemicellulose and cellulose are more prone toward degradation than lignin.
Archeological wood in most cases still present lignin and cellulose that should be preserved from
further degradation. We have developed a method, based on the use of calcium and magnesium
hydroxide nanoparticle in non-aqueous solvents that is very efficient for cellulose deacidification and
protection from acidic and oxygen degradation, even in the presence of transition metal ions (iron and
copper are the most common). Nanoparticles application to Vasa and Oseberg archeological
shipwrecks protects wood toward further acid and oxygen degradation allowing the Conservation of
the ships.
6
J. Guo1, H. Rennhoffer2, Y. Yin1, H. Lichtenegger2
1
Department of Wood Anatomy and Utilization, Research Institute of Wood Industry, Chinese
Academy of Forestry, Beijing 100091, China
2
Institute of Physics and Materials Science, BOKU, 1190 Vienna, Austria
The utilization of wood is often restricted by the lack of dimensional stability due to e.g. moisture
change. Thermo-hygro-mechanical treatment (THM) of wood can significantly improve the physical
properties of wood, including the mechanical behavior and size stability.
One promising THM method is compression of wood combined with steam (CS) treatment. In this work
we investigated the response of the wood cell walls of Chinese fir (Cunninghamia lanceolata) to the CS
treatment by means of X-ray scattering. Wide-Angle X-ray Scattering (WAXS) was used to investigate
the changes of cellulose crystallites dimension, aspect ratio, non-crystalline fraction and the number
of chains in each microfibril and Small-Angle X-ray Scattering (SAXS) was used to determine the fibril
diameter distribution the fractal dimension and size of pores in response to CS treatment conditions.
CS treatment results in increased crystallinity and increased crystal size depending on the CS conditions
for both, early wood and latewood, while the microfibril diameter in wood is not affected. The changes
by CS treatment are attributed to a rearrangement of cellulose chains and also degradation of
amorphous regions as well as the hemicellulose and the lignin at higher temperatures.
7
SESSION 1
The Micro- and Nanoscale structure of heat steam compressed wood
SESSION 1
Non-specific tracking of transport pathways in the nanostructure of wood by
ultra-small nanoparticles using electron microscopy, X-ray scattering, and
confocal Raman imaging
J. Segmehl1, A. Lauria1, T. Keplinger1, J. Berg1, I. Burgert1
1
ETH Zurich, Institute for Building Materials, Wood Materials Science, Zurich, Switzerland
Sustainability and environmental compatibility are increasing concerns of today’s society and are an
important requirement in the development of new materials. A recent approach for the design of such
novel material systems focuses on inspiration by nature. Multifunctionality is frequently found in
nature’s materials and hierarchical structure and material combination could be found to be important
design criteria. To implement similar property combinations in synthetic materials, two main
approaches were followed so far. One approach is the assembly of entirely synthetic structures
through bottom up strategies, where a main drawback is still the upscaling to reach dimensions beyond
the millimetre scale. Another approach is based on the usage of natural materials as structuring
scaffolds for hierarchical organization. Such processes are mainly based on infiltration of the inherent
porous structure and therefore, penetrability and porosity are the main factors impeding the sufficient
addition of a second material phase.
To understand better these limitations in processing, we studied the native percolation pathways and
penetrability in native wood structures, via an ultra-small particle system, based on europium-doped
hafnia. The particles were infiltrated into native wood, allowing to probe for the percolation pathways
present in the unaltered cell wall structure. The multi-functionality of the nanoparticles, e.g. high
electron density, crystallinity, and optical properties, allow their use as universal in situ tracker, as they
can be detected with high spatial resolution using electron microscopy, X-ray scattering, and confocal
Raman imaging. We could show, that based on the small size of the particle system, a full penetration
of the native cell wall structure in wood can be reached and sufficient percolation is present in the
porosity of the native structure.
8
F. di Renzo1, J. Bossu1, P. Trens1, S. Corn2, N. LeMoigne2, T. Zemb3
1
Université Montpellier 2, Institut Charles Gerhardt Montpellier, 34095 Montpellier, France
Centre des Matériaux des Mines d’Alès (C2MA), 30100 Alès, France
3
ICSM, CEA/CNRS/UM2/ENSCM, 30207 Bagnols–sur–Cèze, France;
2
Dimensional stability is a property of primary interest in the science and technology of wood. If the
swelling and shrinkage of wood under variable humidity conditions is at the basis of correct use of
wood materials, the effect of non-aqueous solvents on wood swelling is an important step of processes
of preservation of wood, elaboration of wood-polymer composites, and fractionation of lignocellulosic
resources. Actually, several works have reported an anomalous swelling in mixed water-organics
solvents at intermediate concentrations. This effect, observed in both green and dry wood and
sometimes exploited in technological applications, has never been adequately explained. Our project,
supported by the Labex Chemisyst, aims to understand the mechanisms underlying this phenomenon,
in the view of better describing the molecular interactions involved in wood swelling and improve
existing models of matter diffusion in vegetal biomass. We have brought together laboratories of
physico-chemistry, biomechanics and molecular modeling to approach the swelling process from
different perspectives. In a multi-technique approach, we are analyzing the capacity and kinetics of
sorption from gas and liquid phases, the variation of macroscopical mechanical properties, and the
microscopical modifications in the cell wall during swelling, using mixed solvents of variable
concentrations. Our first results have confirmed a clear synergical effect of water-organic solutions on
the loss of mechanical properties of poplar fibers. Microscopical monitoring of swelling suggests
specific effects of the solvent components on various cell wall layers. Current comparison of the results
with physico-chemical models is aimed to clarify the relative influence of the colligative properties of
the solvent solution and of the specific molecular interactions of each solvent component with the
different lignocellulose components.
9
SESSION 2
Wood abnormal swelling in mixed solvents and influence on mechanical
properties. Towards a better understanding of the molecular interactions
between wood macromolecules and organic liquids?
SESSION 2
Resolving small-angle neutron scattering data to understand the nanoscale
structure of wood
P. Penttilä1, R. Schweins1
1
Institut Laue Langevin, Large Scale Structures group, 38042 Grenoble, France
Small-angle neutron and x-ray scattering (SANS and SAXS) offer valuable tools for characterizing the
complex, hierarchical structure of the plant cell wall and other cellulosic materials. So far, however,
their efficiency has been limited by a poor understanding of the origin of different features observed
in the experimental data. In this work, SANS measurements on three Northern European wood species
in wet and dry states were carried out and the data were analysed based on simple model fitting. Plans
for future experiments in order to link the features of SANS and SAXS data to physical structures more
precisely will be presented.
10
J. F. Gonzales1, J. Sotres1
1
Malmö University, Faculty of Health and Society, Biomedical Science, 20506 Malmö, Sweden
Wood is a natural renewable widely applied building material. However, it is also highly susceptible to
degradation. In this context, one of the environmental parameters of relevance is humidity. The
ambient humidity directly influence the moisture content (MC) of wood. Wood with high MC is
susceptible to insect and fungal attack. Variations in humidity also lead to wood swelling/shrinkage.
The application of suitable coatings, often made of polymers, is the most used strategy to improve the
durability of wood. Coatings can minimize the effect of relative humidity on wood by drastically
reducing the diffusion rate at which water absorption and desorption occurs. Additionally, coatings
provide chemical and wear resistance. However, it is often forgotten that polymer coatings are highly
susceptible to the ambient humidity themselves. Our research focuses on waterborne wood finishes
(consisting both on polyacrylic acids and polyurethanes). Here we show by means of different
techniques such as QCM-D and AFM that the water content, viscoelasticity and stiffness of these
coatings are highly dependent on the ambient humidity. Our future plans include the use of neutron
and X-ray small angle scattering and imaging methods to gain insight into the underlying mechanisms.
11
SESSION 2
Waterborne wood finishes: influence of the ambient humidity on their water
content and viscoelastic properties
SESSION 3
X-ray scattering and atomic force microscopy as a versatile tool to image
cellular structures : possibilities and applications at the ESRF
M. Capron1, T. Grünewald1
1
ESRF, 71, avenue des Martyrs, CS 40220, 38043 Grenoble Cedex 9, France.
The recent advancement on the understanding of biological structures, in particular wood and
cellulosic plants posed new questions on the microfibrillar arrangement, the orientation and the
crystalline state of the building blocks of the plant cell wall. In this talk, we aim at giving on overview
how x-ray scattering imaging can give insights complementary to other methods like neutron
scattering or NMR investigations. The experimental possibilities at ESRF beamlines like ID13 allow to
study biological structures with unprecedented resolution down to the 10s of nm at amazing speed
and resolution by small and wide-angle x-ray scattering (SAXS/WAXS). Due to the high flux of the
instrument, beam damage effects can be mediated by speed in data acquisition and a significant
reduction in the background noise-level.
Whilst X-rays methods are excellent tools to study the bulk properties of a sample, scanning probe
techniques such as AFM (Atomic Force microscopy) give the opportunity to investigate
complementarily other important aspects of the wood cell walls. Variability of the wood cells
distribution, their thickness and properties lead to difficulties in the mechanical studies of wood at the
macroscopic scale. Indeed, at the microscopic level, every tree has its own cellular organisation and
structure that have a strong effect on the behaviour at macroscopic scales. Knowing the structure and
mechanical behaviour at the microscopic scale of wood is nowadays a challenge especially to improve
the multi-scale modelling. The goal of this presentation is to introduce the use of AFM in wood science
and the facilities that the Partnership for Soft Condensed Matter (PSCM) can offer you as well as
corresponding X-ray characterization at ID13. Due to the variety of modes, AFM allows both to
characterize the micro-structure of wood and to measure its micro-mechanical properties,
simultaneously. Important mechanical properties such as contact and indentation modulus can be
calculated from the AFM experimental data which allows for a multimodal investigation scheme
combined with SAXS/WAXS investigations.
12
M. A. Barrett1, C. Teixeira1, N. Grimm1, A. Perkins2, J. Gonthier2, E. Bourgeat-Lami², S. Baudoin2, B.
Demé2, E. Lelièvre-Berna2, T. Hauß1, K. Kiefer1, D. Wallacher1
1
Helmholtz-Zentrum Berlin für Materialien und Energie, Berlin, Germany.
2
Institut Laue-Langevin, Grenoble, France.
Wood is a hygroscopic material, which means that it will gain or lose moisture depending on the
temperature and humidity of the surrounding air. The higher the relative humidity, the higher the
moisture content of the wood. It will also expand or contract according to humidity. For example, if
wood at 10% moisture content is exposed to 25% RH, it will dry to 5% moisture content and will shrink
as it dries.
Controlling humidity before and during wood characterization is therefore a prerequisite. The D16
instrument at the ILL has a long experience of in situ control of humidity for biological samples. From
the simple, temperature controlled chambers containing saturated salt solutions developed in the
80’s, to the 1st chambers developed in the 90’s where the relative humidity can be changed
automatically, and finally to the most recent developments.
In the frame of the European NMI3 JRA on Sample Environments for Soft Matter (NMI3-FP7-JRA-IIWP20) and thanks to a fruitful partnership between ILL and HZB, the new generation of high precision
humidity chambers has been designed and commissioned at the ILL recently. The principle has not
changed since the previous generation but the design – assisted by COMSOL finite element simulations
- has been carried out to reach high-precision temperature control and high insulating capabilities both
required to approach 100% RH.
With the recent upgrade of the D16 and the associated flux increase (x10), equilibration times of
samples have become a critical issue, since typical acquisitions are now shorter than the time required
to equilibrate samples. This is particularly true when a sample is equilibrated at high relative humidity.
It was therefore decided to produce 3 identical and exchangeable chambers to optimise beamtime,
one being on the instrument while two samples can be equilibrated off-line during data collection.
I will present the design of the new chambers, how these are controlled and automated, and how
these recent developments could be applied to investigations of wood structure.
13
SESSION 3
BerILL the new high-precision chamber for in situ control of temperature and
humidity
SESSION 3
ESEM: a tool for the study of wood hydration
R. Podor1, J. Lautru1, A. Barbetta1,2, T. Zemb1, L. Bertinetti2, H. Möhwald2, J. Bossu3,4, N. Le Moigne3,
F. di Renzo4
1
Institut de Chimie Séparative de Marcoule, UMR5257, CEA/CNRS/UM2/ENSCM, 30207 Bagnols–
sur–Cèze, France
2
Max Planck Institute of Colloids and Interfaces, Department of Biomaterials, Research Campus
Golm, Potsdam
3
Ecole des Mines d’Ales – centre C2MA, Alès, France
4
ICGM - Matériaux Avancés pour la Catalyse et la Santé, Montpellier, France
The use of the Environmental Scanning Electron Microscope (ESEM) for the characterization of wood
cells deformation when submitted to Relative Humidity (RH) variations will be the main purpose of the
presentation. The main differences and advantages of the use of the ESEM when compared to the
conventional high vacuum SEM will be first described. Thus, the difficulties of the control of water
vapor and even more of ethanol-water mixtures will be reported. A particular attention will be also
paid onto the difficulties and the optimization of the observation of wood cells using a high energy
focused electron beam.
The second part of the talk will be devoted to the description of in situ experiments (Fig.1) performed
on wood cells, the associated image processing and the data that can be derived from these
experiments (Fig.2).
Figure 1. Image series of wood cells when contacting with a 50%EtOH-50%H2O vapor at T=2°C.
Figure 2. Variation of the area of the part of wood observed in Fig. 1 relative to the first image
recorded.
14
G. Chaumat1, C. Albino1
1
CEA Grenoble, ARC Nucleart, 38054 Grenoble, France
Wood is too rarely used for outdoor applications due to its poor natural resistance, especially it is very
sensitive to the moisture (dimensional instability, rot,…). Coarsely, three industrial treatment
processes, yet used by industry, exist to improve the wood stability towards water.
i) the grafting system by using reactive agent able to react with cellulosic hydroxyl functions of wood
(anhydride of carboxylic acids, epoxide, aldehyde,… ), ii) the thermal treatments with the pyrolysis of
hemicellulose polymers at high temperature (200°C) and iii) the in situ polymerisation of an
hydrophobic resin that leads to a final plastic/wood composite. The first method is expensive because
it needed to use very reactive and toxic chemicals, the second one is limited by a serious drop of
mechanical properties. Consequently, ARC-Nucléart developed since 2010 an original preservation
process of modern wood following the third method by using organic resource obtained from biomass:
glycerol and citric acid. The initial objectives aimed at developing a treatment from available, nontoxic, free of petroleum products and low cost resins The treatment principles consist in: i) dissolving
a large amount of citric acid / glycerol mixture in water to obtain a syrup, ii) performing an
impregnation of wood by the previous citric acid + glycerol syrup following a vacuum/pressure method
and iii) carrying out the in situ polymerisation of the resin according to an esterification reaction
induced by a thermal treatment close to 150°C. This process, so called Cigal R, permits to reach antishrinkage efficiency coefficients close to 60%, i.e. equivalent to values obtained for grafting and pure
thermal treatment industrial methods. This improvement of dimensional wood stability comes from a
swelling effect of the wood after Cigal R treatment.
It appears that a part of citric acid / glycerol resin succeeded in diffusing in the cell walls. To understand
the interaction mechanisms present in the cell walls, it could be interesting to determine, at the
molecular scale, the quantity of resin trapped by the cell walls, its location in the cell walls and the type
of interaction between the exogenous resin and the constitutive polymers of wood. Is it a copolymerisation with the alcohol functions of cellulosic polymers or just a simple impregnation with
hydrogen bonding? The answers to these questions would be useful to optimize the preservation of
wood treatment, particularly to assess its long-term durability.
15
SESSION 3
Development of a new conservation treatment of wood for outdoor
applications
SESSION 3
Neutron imaging PEG-treated archaeological wood from the Mary Rose: the
role of a hydrogel on a degraded cellular structure
E. Piva1, E. Schofield, D. Derome3, G. Desmarais3
1
Portsmouth University, School of Civil Engineering and Surveying, Portsmouth PO1 3AH, UK
Portsmouth University, Mary Rose Trust, Portsmouth PO1 3AH, UK
3
EMPA, Applied Wood Materials Laboratory, Dübendorf, Switzerland
2
The Mary Rose, flagship of Henry VIII fleet, is nowadays the only surviving Tudor warship. Sunk during
a battle against the French fleet in 1545, she was recovered from the seabed outside Portsmouth
Harbour in 1982. After spending 437 years under the sea bed, the Mary Rose is a time capsule giving a
unique insight into Tudor life. To preserve this important shipwreck for future generations, the wood
has been consolidated with polyethylene glycol (PEG). PEG is a polymer used to mechanically stabilise
archaeological waterlogged wood, and to minimise collapse and shrinkage of the wood cells upon
drying. It took 19 years to spray the ship hull with two grades of PEG (200 and 2000) and finally in May
2013 the Mary Rose started the drying process under controlled environmental conditions (19degC,
54%RH). The success of this phase is critical as it is during this time: despite the PEG treatment of the
wooden timbers, cracking, shrinkage and collapse of the wood cells can occur due the loss of both free
and bound water during the drying phase. Monitoring the moisture content (%MC) of the wood allows
us to evaluate the drying progress, to predict the drying rate and to understand the resulting impact
these will have on the mechanical properties of wood and on the movement currently taking place on
the ship structure.
To further our understanding of the material properties and water sorption and desorption
mechanisms in presence of PEG, we successfully used thermal neutron radiography on Mary Rose
wood samples. Neutron imaging provides unique information that it is not possible to collect using
other techniques: it allows us to spatially resolve the location of the water within the samples during
sorption and desorption experiments. Our objectives were to determine the water diffusion
coefficients while also documenting the swelling/shrinkage and cellular structure deformation in
archaeological wood during controlled desorption. As the Mary Rose is impregnated with both grades
of PEG, it is important to understand if any differences occur in the drying behaviour of archaeological
wood with this conservation treatment. In addition, archaeological wood has different degrees of
degradation between the superficial layer and inner parts, which could cause completely different
water-PEG-wood interaction mechanisms that need to be observed. Differences in drying rate and
shrinkage pattern were documented in the archaeological wood treated with either PEG 200 or PEG
2000 or without PEG treatment, and at varying degrees of degradation. The findings can be relevant
not only for Mary Rose wood but for any waterlogged material that retains water. This critical
information will be used to inform future drying, storage and potential treatments that will ensure the
long term stability of the ship.
16
W. Kunz1, A. Freyburger1, Y. Duan2, C. Zollfrank2
1
Institute of Physical and Theoretical Chemistry, University of Regensburg, 93040 Regensburg,
Germany
2
Chair of Biogenic Polymers, TU Munich, 94315 Straubing, Germany
Cellulose and Lignin are most abundant polymers from natural wood. They have many promising
application properties, but also some drawbacks. To transform cellulose to materials such as fibers or
packaging films, often the viscose has been used (and in part is still used in developing countries). This
process is harmful for the environment. Further, the obtained materials are neither gas- nor
watertight. Lignin is an interesting chemical consisting of valuable aromatic molecules. It is also a
promising support and building material, but it is brittle and not flexible. To improve the properties of
these most relevant wood components, we tried to combine it with chitin, another abundant, natural
polymer.
The challenge was to find a solvent to dissolve simultaneously both cellulose and chitin or lignin and
chitin. From these mixtures, we prepared hybrid bulk materials and also cellulose materials covered
by a thin film of chitin. As a result, we obtained e.g. cellulose-based materials with a significantly
increased water-resistance and lignin-based materials with a considerable flexibility. In the present
contribution, I will report on the production process as well as on the materials’ properties.
17
SESSION 4
Cellulose/Chitin and Lignin/Chitin Hybrid Materials
SESSION 4
Oriented Crystallization of Barium Sulfate Conned in Native Wood Structures:
a High-Resolution Study via Scanning Wide-Angle X-ray Scattering
J. Berg1,2, V. Merk1,2, C. Krywka3, I. Burgert1,2
1
ETH Zurich, Institute for Building Materials, Wood Materials Science, Zurich, Switzerland
EMPA, Applied Wood Materials Laboratory, Dübendorf, Switzerland
3
Helmholtz Zentrum Geesthacht (HZG), Institute for Materials Research, X-ray Imaging with
Synchrotron Radiation, HZG Outstation at DESY in Hamburg, Geesthacht, Germany
2
In Nature, biomineralization comprises the directed formation of inorganic minerals within an organic
scaffold. The synthetic mimicry of these processes, while challenging, presents the possibility to both
learn about the fundamentals of biogenic mineralization and to control the synthesis of novel hybrid
materials. Natural, porous material, such as wood, is an attractive option as an organic scaffold,
offering hierarchical porosity and crystalline cellulose native to the wood cellular structure, essential
for the study of crystallization under confinement and template-assisted growth. In this work, we
present the precipitation of barium sulfate in the micro- and nanopores of native wood cells and cell
walls. Through various spatially resolved measurement techniques, e.g. confocal Raman spectroscopic
imaging, scanning electron microscopy, and synchrotron scanning wide-angle X-ray scattering, the
crystalline morphology and orientation could be followed in the wood structure over various length
scales.
While dendritic barite crystals in the microscale cell lumina suggested heterogeneous growth from the
wood cell wall interfaces, barite inside the nanoporous cell walls demonstrated a crystallographic coorientation with the crystalline cellulose, indicating an epitaxial growth. Further control of this
biomimetic mineralization may open new possibilities for hierarchically structured hybrid materials.
18
G. Chaumat1, T. Guiblain1, L. Meunier-Salinas1
1
CEA Grenoble, ARC Nucleart, 38054 Grenoble, France
Museums and main worldwide preservation workshops specialized in the treatment of the
archaeological organic materials have been confronted for these last years with a phenomenon of
“leprosy” which questions treatments used to treat the wooden wet archaeological objects. The rashes
which appear on objects after treatment are due to the presence of unstable salts. After drying of the
object and in the contact of the air, these salts compounds oxidize to cause the swelling and cracking
of the wood and lead to a catastrophic acidification of the material by sulfuric acid (pH < 2). The most
symbolic case of the acid attack of the wood is represented by the famous Swedish warship Vasa (17th
century) at the museum of Stockholm: approximately 2 tons of acid are considered present in the
whole ship. Similar situations exist with the famous Mary Rose English warship (16th) treated actually
in Portsmouth. In the same way, ARC-Nucléart is confronted in the last years with this problem after
the collection of objects from the Italian wreck of the 16th century La Lomellina, discovered at
Villefranche-sur-Mer. A frog of halyard three meters long, riddled with corroded nails, presented such
outbreaks a few months after its drying. Roman river ships excavated in Arles and Lyon (2nd D.C.) for
which systematic pyrite (FeS2) disseminations were found close to the steel nail spots. Numerous
studies led by scientific teams worldwide have been dealing with ageing of ferrous salts and extensive
analytical characterizations to determine the different chemicals in presence. Nevertheless, the
scientific works focused on the neutralization (curative action) and passivation of pyrite (preventive
action) is less represented. Indeed, the main constraint comes from the difficulty to observe in situ the
different phenomena that occur in the volume of the wood: • The localization of pyrite and other sulfur
base products in the wooden artefacts. • The diffusion of the tested active principles in the porosity of
the wood structure, and more hardly in the intimacy of the cell wall. • The chemical activity of these
compounds with the ferrous salts: in situ interface study with pyrite crystals and reactants, presence
or not of humidity due to water sorption by sulfuric acid, the pH level in the wooden pores.
19
SESSION 4
Acidification of treated composite archaeological artifacts
SESSION 5
An equation of state approach to describe water sorption, swelling and
passive actuation of secondary cell walls
L Bertinetti1, T. Zemb2, P. Fratzl1, A. Barbetta2
1
2
Max Planck Institute of Colloids and Interfaces, 14424 Potsdam, Germany.
ICSM, CEA/CNRS/UM2/ENSCM, 30207 Bagnols–sur–Cèze, France;
Wood consists of parallel cylindrical cells. The so-called “wood material”, i.e. the materials the cell
walls are made of, is a complex, highly anisotropic and hierarchically organized nanocomposite,
characterized by stiff crystalline cellulose nanofibers parallel to each others embedded in a matrix of
a much softer, less anisotropic gel of hemicelluloses and lignin. The matrix is hygroscopic and swells
with increasing relative humidity. Consequently, wood cells undergo significant dimensional changes.
Although this represents a major technological challenge and more of 80 sorption isotherms models
have been proposed to describe the wood swelling over more than 100 years, a model that takes into
account the structure and composition of the material, able to quantitatively give reason for the
thermodynamics of the phenomenon, still does not exist. We developed a minimal parameter-free
model of wood secondary cell walls to predict water absorption, in the form of an Equation of State
(EOS). The EOS takes into account several opposite mechanisms: hydration force of water around
fibres of cellulose and partial entropy of mixing versus “contact points”, i.e. free energy associated to
hemicellulose (soft) cross-linking cellulose crystals . Because the wood is a nanocomposite material in
which the fibers act as an external constraint with respect to the swelling matrix, the mechanical
energy to deform the composite upon swelling was also taken into account. Hysterisis is not predicted
but water uptake versus humidity is reproduced in a large temperature range, and origin of wood
dissolution in strong bases and hydrophobisation by adsorption of weak fatty acids are qualitatively
explained at a molecular level. Also, this model can account for electrostatic contributions and
captures the behaviour of cell walls when in contact with electrolytic solutions. Finally, as this force
balance approach describes the full energetics of water-cell walls interactions, it can be used to
describe the actuation and force generation possibilities of secondary cell walls on which many
organisms rely to accomplish vital functions.
In this contribution, we present a thermodynamic modelling, based on a force balance approach, able
to predict water sorption and swelling of wood secondary cell walls.
20
J. Schwiedrzik1, R. Raghavan2, M. Rüggeberg3, S. Hansen4, J. Wehrs1, R. Adusumalli5, T. Zimmermann6,
J. Michler6
1
EMPA, Swiss Federal Laboratories for Materials Science and Technology, Thun, Switzerland
University of California, Santa Barbara, CA 93106-5050
3
ETH Zurich, Institute for Building Materials, Wood Materials Science, Zurich, Switzerland
4
KIT, Inst Biol Interfaces, Eggenstein Leopoldshafen, Germany
5
BITS Pilani Hyderabad Campus, Department of Chemical Engineering, Hyderabad, Andhra Pradesh,
India
6
EMPA, Applied Wood Materials Laboratory, Dübendorf, Switzerland
2
1. Introduction
Many biological materials feature a hierarchical architecture with remarkable mechanical properties
combining low weight with both toughness and strength. In order to better understand the
mechanisms leading to this unusual combination of traits, structure-property relationships have to be
assessed on all length scales. Wood is such a hierarchical material. Its cell walls feature semi-crystalline
cellulose fibrils embedded in an amorphous polymer network that are aligned at an angle to the cell
main axis. Continuum micromechanics can predict mechanical behavior on a higher length scale based
on the composition, microstructure, and properties of the individual phases. However, the
experimental data for yield properties at the microscale is sparse making an identification of phase
properties and validation of yield predictions difficult. Specifically, the lignin yield strength in wood
remains to be measured, which proves to be difficult due to the intermixed nature of the polymer
network and the small length scales involved. Inverse determination of phase properties from
experiments on a higher length scale is possible using continuum micromechanics, if composition,
microstructure, and boundary conditions are sufficiently well understood. An experimental setup for
micromechanical testing with well-defined boundary conditions is micropillar compression [1]. Micron
sized pillars are eroded from bulk material using a focused ion beam and compressed uniaxially using
a flat punch indenter. Due to the mostly homogeneous and uniaxial loading conditions, the setup may
be combined with continuum micromechanics to access phase properties at a lower length scale.
2. Results
In this work, micropillar compression tests were used leading to homogeneous and uniaxial stress
fields on a single cell wall layer for normal and compression wood of Norway spruce. Additionally, the
chemical composition was determined by wet chemical analysis and the cellulose fibril angle
distribution was measured using wide angle XRD. Subsequently, an existing continuum
micromechanics model for elastic limit states [2] was adapted to explain the measured microscale
properties and to relate them to species-independent phase properties on a lower length scale, more
specifically the lignin yield stress [3]. The micropillar compression experiments showed a highly ductile
behavior of the wood cell wall. While the maximum stress reached in both tissues was rather similar,
compression wood yielded at much lower stress levels and showed more strain hardening and an
increased ductility compared to normal wood. This may be explained by the differences in chemical
composition and MFA. Taking these differences into account, the micromechanical model was able to
reproduce the inter-group variation observed experimentally within the boundaries set by modeling
assumptions and experimental error. The model was then used to identify the yield strength of lignin,
which was found to be 15.7 MPa in normal and 18.0 MPa in compression wood. Using an average lignin
strength of 17 MPa, the model was able to reproduce the experimentally determined median yield
21
SESSION 5
Identification of lignin yield stress in the wood cell wall by a combination of
micropillar compression, WAXD, wet chemical analysis and micromechanical
modeling
SESSION 5
points very well. It could thus be verified by two independent experiments on a lower length scale that
the in situ yield stress of lignin in wood is approximately 17 MPa.
3. Conclusions
The study demonstrates a novel approach for measuring phase properties of inhomogeneous
materials by a combination of continuum micromechanical modeling with chemical and
microstructural analysis and micropillar compression experiments inside a scanning electron
microscope under controlled conditions. The mostly homogeneous and uniaxial stress state in this
experimental setup allows to identify yield stresses at the microscale and to assess phase properties
on a lower length scale with high accuracy and reproducibility if the microstructure and the inelastic
deformation mechanisms of the tested material are well understood. The in situ lignin strength in
wood could thus be measured by two independent tests giving consistent results. This could be an
interesting approach for validating multiscale models or identifying phase properties for other
nanostructured materials in the future.
References
[1] Adusumalli et al., Applied Physics A 100 (2), 2010 [2] Hofstetter et al., Mech Adv Mat Struct 15 (67), 2008. [3] Schwiedrzik et al., Phil Mag 96 (32-34), 2016
22
M. Bardet1, Q.-K Tran1
1
CEA, INAC, SCIB/LRM, 38054 Grenoble, France
High-resolution solid-sate 13C NMR is a powerful tool to study structural and dynamics of
lignocellulosic materials and their derivatives [1,2]. As a matter of fact the proton to carbon cross
polarisation (CP) transfer combined with fast spinning (several kHz) of the samples at the magic angle
spinning (54.7° related to the vertical magnetic field) lead to record distinct NMR signal for each carbon
with different chemical surroundings. Solid state NMR is also sensible to tridimensionnal structures
leading to information on crystalline or amorphous state of products. In this presentation the
application of NMR to study archaeological wood is presented [3]. It allows to evaluate the state of
degradation of the samples. For instance in the case of waterlogged wood we have shown that
hemicelluloses are first degraded and then celluloses. Lignins appear to be much more resistant in such
water rich environment.
For their long term conservation, archaeological wood are treated with polyethylene glycol (PEG 2000
or 4000 molecular weight) and NMR can be used to study the hybrid material. Using 13C magnetization
build-up under CP to measure T1gH , we are able to study the interactions at a molecular level between
PEG and residual wood components, either lignins or celluloses. Very interestingly we demonstrated
that only a certain amount of PEG was interacted with wood components [4,5]. This amount is strongly
dependent on the degree of degradation of samples. In the case of little degraded wood we showed
that some properties of the cell walls can be restored since the PEG can enter the microfiber and fill
the free volumes due to hemicelluloses depletion. Such solid-state NMR approach can be employed to
characterized wood-derived materials for green electronics, biological devices and energy applications
[6-9].
[1] Bardet, M.; Foray, M. F.; Tran, Q. K. Analytical Chemistry 2002, 74, 4386-4390.
[2] Bardet, M.; Pournou, A. Annual Reports on NMR Spectroscopy 2017, 90, 41-77.
[3] Bardet, M.; Foray, M. F.; Maron, S.; Goncalves, P.; Tran, Q. K. Carbohydr. Polym. 2004, 57, 419-424.
[4] Bardet, M.; Gerbaud, G.; Tran, Q. K.; Hediger, S. Journal of Archaeological Science 2007, 34, 16701676.
[5] Bardet, M.; Gerbaud, G.; Doan, C.; Giffard, M.; Hediger, S.; De Paepe, G.; Tran, Q. K. Cellulose 2012,
19, 1537-1545.
[6] Bardet, M.; Hediger, S.; Gerbaud, G.; Gambarelli, S.; Jacquot, J. F.; Foray, M. F.; Gadelle, A. Fuel
2007, 86, 1966-1976.
[7] Melkior, T.; Jacob, S.; Gerbaud, G.; Hediger, S.; Le Pape, L.; Bonnefois, L.; Bardet, M. Fuel 2012, 92,
271-280.
[8] Bardet, R.; Reverdy, C.; Belgacem, N.; Leirset, I.; Syverud, K.; Bardet, M.; Bras, J. Cellulose 2015, 22,
1227-1241. [9] Melkior, T.; Barthomeuf, C.; Bardet, M. Fuel 2017, 187, 250-260.
23
SESSION 5
Structural analysis and Dynamics Properties of Archaeological Wood with
High-Resolution Solid-State 13C NMR
SESSION 5
Mechanical stresses and moisture changes in wood assessed at molecular
level with near infrared spectroscopy
J. Sandak1, A. Sandak1
1
IVALSA, CNR, Trees and Timber Institute, 38010 San Michele All Adige, Italy
Wood is a complex natural composite consisting of different polymers. The interaction between these
polymers varies when applying mechanical or moisture stresses. Near infrared spectroscopy (NIRS) has
been proved as a highly usable tool for characterization of wood, with especially useful capability for
assessing functional groups of woody polymers. An important advantage of this technique is that
hydroxyl groups of lignin, cellulose and hemicellulose involved in moisture sorption are distinguishable
and spectral absorption bands are distributed at different light wavelengths. As a consequence, it
allows detailed analysis of the sorption kinetics, including differentiation of the involved polymers. On
the other hand, the wood deformations affected by applying mechanical stresses results is changes of
molecular configurations, being also detectable by near infrared. The goal of this work is to present
some results from the several tests where wood at different moisture and mechanical stresses was
assessed with NIR spectroscopy. Such knowledge may be highly useful for understanding of the
mechanisms of the materials responses to stresses and can be therefore used for improving numerical
models related.
24
B. Medronho1
1
University of Algarve, Faculty of Sciences and Technology, MEDITBIO, 8005-139 Faro, Portugal
As the major carbohydrate produced by plant biosynthesis, cellulose occupies a prominent place as a
‘green’ polymer for the production of innovative and sustainable materials. Unlike other polymers,
cellulose is not meltable and therefore most of it applications rely on an efficient dissolution step
followed by shaping processes where the properties of the regenerated material are strongly
dependent on how well cellulose is dissolved and organized in solution. Already in the wood cell wall,
such organization of the different molecules (involving aggregates of cellulose in microfibrils together
with other matrix components such as hemicelluloses and lignin) is determinant for the plant structural
properties. Here we demonstrate that Polarization Transfer Solid State NMR (PT ssNMR) emerges as
promising technique regarding an efficient and robust characterization of the solution state of
cellulose.
With this method it is possible to identify the liquid and solid fractions of cellulose, the degradation
products, cellulose polymorphs, etc. Finally, combining static light and small angle X-ray scattering, the
effect of cellulose aggregation on solution rheology is assessed.
25
SESSION 6
Advances in cellulose dissolution: From scattering and rheology to a new
NMR approach
SESSION 6
Heterogeneous swelling and dissolution of cellulosic fibres in aqueous
solvents: role of cell walls and supramolecular structure
P. Navard1, N. Le Moigne2
1
2
CEMEF, MINES ParisTech - CNRS UMR 7635, 06904 Sophia Antipolis, France
Centre des Matériaux des Mines d’Alès (C2MA), 30100 Alès, France
Cellulose is a major source of raw material for paper, films, textile and composite industries as well as
derivatives for food, paints, cosmetics or pharmaceuticals applications. It is extracted from native
ligno-cellulosic fibres that are complex hierarchical bioassemblies made of various biopolymers
(polysaccharides, lignin, proteins. . . ) organized in several concentric cell wall layers. These specific
structures are of great interest to build up new bio-based materials. However, they exhibit complex
behaviour during processing such as differential swelling and dissolution capacity in solvents. Despite
advanced knowledge in the chemical modification and dissolution of cellulosic fibres, the role of their
microstructural and macromolecular organization on the swelling and dissolution mechanisms still
remain a complex scientific field.
The focus of this work was to study the swelling and dissolution of cellulosic fibres under various
conditions, in particular by varying the quality of the solvent (N-methylmorpholine-Noxide with various
amount of water, NaOH 8% / water). Based on high resolution microscopic observations, selective
separation of insoluble fractions and molar mass distribution and sugar composition analyses, we were
able to better describe the characteristic mechanisms of swelling and dissolution of cellulosic fibres at
the different scales of their structure, i.e. from the cell walls down to the macromolecular level. Our
results demonstrate the existence of a gradient in dissolution capacity within the cell walls and
highlight the importance of the chemical environment and molecular mobility of cellulose chains
towards swelling and dissolution.
26
D. Derome1, C. Zhang1, J. Carmeliet2
1
2
EMPA, Applied Wood Materials Laboratory, Dübendorf, Switzerland
ETH Zurich, Institute for Building Materials, Wood Materials Science, Zurich, Switzerland
Water absorption in porous media presents many different facets, from the complex configuration of
water in the porous structures, the rearrangement induced by the vapor sorption into polymeric
structures and the influence on the physical properties of the material. We present these phenomena
as they interact in wood, a multi-scale polymeric composite material. The work carried out by
simulation on the nanometer scale is related to the hygroscopic behavior of the wood observed at
cellular scale by X-ray microtomography.
In the vapor phase, we study the role of moisture on the structure and physical properties of the
amorphous biopolymers. We model the sorption of water in cellulose, hemicellulose and lignin (wood
cell wall components) at the nanometer scale with molecular dynamics, and study the implication on
swelling and mechanical properties, linking to the swelling of wood as cellular material. The upscaling
and observations are carried out using a poromechanical approach, which is a rigorous means of taking
into account the interaction of fluids with the solid matrix in porous materials.
Six representative model structures are present in layer S2 of the wood cell wall: crystalline cellulose,
amorphous cellulose, galactoglucomannan (hemicellulose), lignin, cellulose microfibril and microfibril
aggregate (ersatz for layer S2). The MD models have been studied over the full range of moisture
content, from dry to fully hygroscopically saturated. The size of a simulated structure is of the order of
a few nanometers and the sampling time reaches 20 ns. The obtained adsorption isotherms,
mechanical moduli, swelling coefficient, heat of sorption and diffusion coefficients show a good
agreement with the experimental results obtained on wood or its components. The results show that
the effects of moisture sorption in biopolymers can be captured at the nanometric scale.
At the beginning of adsorption, the polymer material shows a slight swelling and an increase in porosity
while the available free volume per molecule of water decreases. The porous structure is characterized
mainly by pores with a size of <1 nm and the distribution of the moisture in the material is more or
less uniform. The mechanical properties change little and the diffusion coefficient is low as long as one
molecule does not undergo the presence of other water molecules. At the same time, the heat of
adsorption is high due to strong hydrogen bonds. For higher moisture content, the porosity and total
volume increase linearly with moisture content and a strong impact on mechanical properties is
observed.
27
SESSION 6
Absorption in wood: capturing all the effects by MD
SESSION 6
High-resolution structure of cellulose to the nanostructure of wood: neutron
/ X-ray scattering and molecular modeling
Y. Nishiyama1, Y. Ogawa1, T. Kuribayashi2
1
2
CERMAV, CNRS, 38041 Grenoble, France
Tokyo University, Graduate School of Agricultural and Life Science, Tokyo 1138657, Japan
X-ray and neutron scattering has been crucial in the determination of detailed crystal structure of
cellulose allomorphs at atomic resolution using model samples. These structures allowed validations
of quantum chemical calculation and validation/adaption of force-fields for molecular modeling used
to simulate cellulose microfibrils and interaction with hemicellulose. The small diameter of cellulose
microfibrils, typically of a few nanometers, results in very broad diffraction signal in the equatorial
direction. Due to the unresolved scattering features, we cannot deduce the structural detail of wood
from the diffraction only, but the modeling capacity allows us a rational approach that can be
controlled by confrontation with scattering data.
The lateral dimension of the cellulose microfibrils and their spatial arrangements are closely related to
the biosynthetic mechanisms and the material properties. Current model of cellulose synthase
complex contains 18 catalytic domains but the apparent crystal dimensions estimated from the
diffraction line broadening are significantly larger. Building explicit model with surrounding
environment allowed us to solve the apparent contradiction as the non-crystalline surrounding also
contributed constructively to the low-resolution diffraction.
Recent results on in-situ SAXS/WAXS experiments on the structure evolution during (hydro- ) thermal
treatments, emulating the situation in kiln-drying, thermal wood process or pulping process will be
also presented.
28
S. Tapin-Lingua1, K. Ruel2, J.-P. Joseleau2, D. Messaoudi, M. Petit-Conil1
1
FCBA, InTechFibres, Domaine universitaire CS 90251, 38044 Grenoble, France
LINK Conseil, 38570 Le Cheylas, France
3
Berkem Développement, 33290 Blanquefort, France
2
The preservative efficacy of organic biocides is strongly related to their capacity of penetration and
retention within wood tissues. The specific detection of the pyrethroid insecticide cypermethrin is
currently obtained after extraction followed by chemical analysis by chromatography techniques.
However visualizing the insecticide molecule within the wood structure requires specific probes
together with microscopy techniques. Therefore, the aim of the present work was to apply a new
methodology based on antibody-antigen recognition and electronic microscopy to visualize directly
cypermethrin in wood material. A polyclonal antibody directed against cypermethrin was developed
and implement it on Pinus sylvestris wood samples coated with technical cypermethrin. The antibody
was tested on cypermethrin-impregnated wood and the specific recognition of the insecticide was
visualized in transmission electron microscopy (TEM). The immunogold-TEM assay evidenced the
capacity of the synthetic biocide to penetrate in the wood. The depth of penetration was measured on
sections taken at increasing distances from the coated surface of the wood. Such results correlated
with chemical analyses carried out by GC-ECD after extraction. In addition, the immuno-TEM
investigation allowed visualizing, for the first time at the ultrastructure scale of resolution, that
cypermethrin was able to diffuse within the secondary wood cell walls.
29
SESSION 6
Development of a new characterization method to analyse Cypermethrin
penetration in wood material by immunolabelling
LIST OF PARTICIPANTS
30
BAGLIONI
Piero
[email protected]
Dept Chimica "Ugo Schiff",
Firenze
Univ Firenze
Italy
BARDET
Michel
[email protected]
CEA, INAC
France
BERG
John
[email protected]
BERTINETTI
Luca
[email protected]
ETH Zurich
Zurich
Max Planck of Colloids and
Potsdam
Interfaces
BOSSU
Julie
[email protected]
Institut Charles Gerhardt
Montpellier
Montpellier France
BOUDOU
Caroline
[email protected]
ILL
Grenoble
France
CAPRON
Marie
[email protected]
ESRF, PSCM
Grenoble
France
CHAUMAT
Gilles
[email protected]
ARC-Nucléart, CEA
Grenoble
France
CRISTIGLIO
Viviana
[email protected]
Institut Laue Langevin
Grenoble
France
DEMÉ
Bruno
[email protected]
Institut Laue-Langevin
Grenoble
France
DEROME
Dominique
[email protected]
EMPA
Dübendorf Switzerland
DI RENZO
Francesco
[email protected]
Institut Charles Gerhardt
Montpellier France
Grenoble
Switzerland
Germany
DOLLIÉ
Lucas
[email protected] LGP2
SaintMartinD'hères
FROMENT
Karine
[email protected]
ARC-Nucléart
Grenoble
France
GABRIEL
JeanChristophe
[email protected]
CEA
Grenoble
France
GONZALES
Juan Francisco [email protected] Malmö University
Malmö
Sweden
GRILLO
Isabelle
GRÜNEWALD Tilman
France
[email protected]
Institut Laue Langevin
Grenoble
France
[email protected]
ESRF
Grenoble
France
GUIZANI
Chamseddine [email protected]
LGP2 Grenoble
Gières
France
HESS
David
[email protected]
Institut Laue Langevin
Grenoble
France
JOHNSON
Mark
[email protected]
Institut Laue Langevin
Grenoble
France
KUNZ
Werner
[email protected]
Institute of Physical and
Theoretical Chemistry,
Regensburg Germany
University of Regensburg,
LAUTRU
Joseph
[email protected]
ICSM
31
Bagnols Sur
France
Cèze Cedex
LECOURT
Michael
[email protected]
LE MOIGNE
Nicolas
MADER
Grenoble
France
[email protected] Ecole des mines d'Ales
Ales
France
Alison
[email protected]
ILL
Grenoble
France
MEDRONHO
Bruno
[email protected]
University of Algarve
Faro
Portugal
NISHIYAMA
Yoshiharu
[email protected]
CNRS
Gieres
France
PASSAS
Raphaël
[email protected]
inp.fr
St Martin
D'hères
France
PENTTILÄ
Paavo
[email protected]
Institut Laue-Langevin
Grenoble
France
PIVA
Eleonora
[email protected]
Portsmouth University
PODOR
Renaud
[email protected]
ICSM
Portsmouth England
Bagnols sur
France
Cèze
PONTONI
Diego
[email protected]
ESRF PSCM
Grenoble
France
PRÉVOST
Sylvain
[email protected]
Institut Laue Langevin
Grenoble
France
RENNHOFER
Harald
[email protected]
Institute of Physics and
Materials Science, BOKU,
Vienna
Vienna
Austria
SANDAK
Jakub
[email protected]
CNR-IVALSA
SCHOFIELD
Eleanor
[email protected]
Mary Rose Trust
San Michele
Italy
All'adige
Portsmouth England
SCHWEINS
Ralf
[email protected]
Institut Laue Langevin
Grenoble
France
SCHWIEDRZIK Jakob
SEGMEHL
Jana
SUSINI
Jean
[email protected]
[email protected]
[email protected]
EMPA
ETH Zurich
ESRF
Thun
Zurich
Grenoble
Switzerland
Switzerland
France
TAPIN-LINGUA Sandra
[email protected]
FCBA
Grenoble
France
TRAN
Khoi
[email protected]
CEA ARC-NUCLEART
Grenoble
France
ZEMB
Thomas
[email protected]
ICSM
Bagnols sur
France
Cèze
32
FCBA
33