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

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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 : chemwood@ill.fr

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PROGRAMME

23 March 2017

Sess

ion

1

8:45 -9:00 Opening T. Zemb, ICSM deputy director, Marcoule, France Page

9:00 -9:40 Invited contribution

P. Baglioni Conservation of archeological wood: the Vasa and Oseberg case studies

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9:40 -10:05 Oral 1 H. Rennhofer The Micro-and Nanoscale structure of heat steam compressed wood

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10:05 -10:30 Oral 2 J. Segmehl 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

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10:30 -10:45 Coffee break

sess

ion

2

10:45 -11:25 Invited contribution

F. di Renzo

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?

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11:25-11:40 Oral 3 P. Pentillä Resolving small-angle neutron scattering data to understand the nanoscale structure of wood

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11:40 -12:00 Oral 4 J.F. Gonzales Waterborne wood finishes: influence of the ambient humidity on their water content and viscoelastic properties

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12:00 -13:45 Lunch

13:45 – 14:00

M. Johnson, J. Susini

ILL –ESRF, the director’s word

Sess

ion

3

14:00 -14:35 ESRF contribution

M. Capron, T. Grünewald

X-ray scattering as a versatile tool to image cellular structures : Possibilities and applications at the ESRF

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14:35 -15:00 ILL contribution

B. Demé BerILL the new high-precision chamber for in situ control of temperature and humidity

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15:00 -15:25 ICSM Contribution

R. Podor-J. Lautru

Environmental microscopy under humidity control

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15:25 -15:50 Oral 5 G. Chaumat Development of a new conservation treatment of wood for outdoor applications

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15:50 -16:15 Oral 6 E. Piva Neutron imaging PEG-treated archaeological wood from the Mary Rose: the role of a hydrogel on a degraded cellular structure

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16 :15 -17:30 Coffee break and discussion

Sess

ion

4

17:30 -18:10 Invited contribution

W. Kunz Cellulose/chitin and lignin/chitin hybrid materials

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18:10 -18:35 J. Berg

Oriented crystallization of barium sulfate confined in native wood structures: a high-resolution study via scanning wide-angle X-ray scattering

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18:35 -19:00 Oral 8 G. Chaumat Acidification of treated composite archaeological artifacts

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19:45 Workshop dinner Fantin LaTour

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24 March 2017

Sess

ion

5

8:30 -9:10 Invited contribution

L. Bertinetti An equation of state approach to describe water sorption, swelling and passive actuation of secondary cell walls

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9:10 -9:35 Oral 9 J. Schwierdzyk

Identification of lignin yield stress in the wood cell wall by a combination of micropillar compression, WAXD, wet chemical analysis and micromechanical modeling

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9:35 -10:00 Oral 10 M. Bardet Structural analysis and dynamics properties of archaeological wood with high-resolution solid-state 13C NMR

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10:00 -10:25

Oral 11 J. Sandak Mechanical stresses and moisture changes in wood assessed at molecular level with near infrared spectroscopy

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10:25 -10:30

Coffee break

sess

ion

6

10:40 -11:20

Invited contribution

B. Medronho Advances in cellulose dissolution: From scattering and rheology to a new NMR approach

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11:20 -11:45

Oral 12 N. Le Moigne Heterogeneous swelling and dissolution of cellulosic fibers in aqueous solvents: role of cell walls and supramolecular structure

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11:45 -12:10

Oral 13 D. Derome Absorption in wood : capturing all the effects by MD

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12:10 -12:35

Oral 14 Y. Nishiyama High-resolution structure of cellulose to the nanostructureof wood: neutron / X-ray scattering and molecular modeling

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12:35 -12:50

Oral 15 S. Tapin-Linga Development of a new characterization method to analyse cypermethrin penetration in wood material by immunolabelling

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12:50 -13:00

Conclusion ... then lunch

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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.

SESS

ION

1

7

The Micro- and Nanoscale structure of heat steam compressed wood

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.

SESSION

1

8

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.

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ION

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9

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?

F. di Renzo1, J. Bossu1, P. Trens1, S. Corn2, N. LeMoigne2, T. Zemb3 1 Université Montpellier 2, Institut Charles Gerhardt Montpellier, 34095 Montpellier, France 2 Centre des Matériaux des Mines d’Alès (C2MA), 30100 Alès, France 3 ICSM, CEA/CNRS/UM2/ENSCM, 30207 Bagnols–sur–Cèze, France;

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.

SESSION

2

10

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.

SESS

ION

2

11

Waterborne wood finishes: influence of the ambient humidity on their water

content and viscoelastic properties

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.

SESSION

2

12

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.

SESS

ION

3

13

BerILL the new high-precision chamber for in situ control of temperature and

humidity

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-II-

WP20) 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.

SESSION

3

14

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.

SESS

ION

3

15

Development of a new conservation treatment of wood for outdoor

applications

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, non-toxic, 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 anti-shrinkage 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 co-polymerisation 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.

SESSION

3

16

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 2 Portsmouth University, Mary Rose Trust, Portsmouth PO1 3AH, UK 3 EMPA, Applied Wood Materials Laboratory, Dübendorf, Switzerland 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.

SESS

ION

3

17

Cellulose/Chitin and Lignin/Chitin Hybrid Materials

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.

SESSION

4

18

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 2 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

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 co-

orientation with the crystalline cellulose, indicating an epitaxial growth. Further control of this

biomimetic mineralization may open new possibilities for hierarchically structured hybrid materials.

SESS

ION

4

19

Acidification of treated composite archaeological artifacts

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.

SESSION

4

20

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 Max Planck Institute of Colloids and Interfaces, 14424 Potsdam, Germany. 2 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.

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Identification of lignin yield stress in the wood cell wall by a combination of

micropillar compression, WAXD, wet chemical analysis and micromechanical

modeling

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 2 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 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

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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 (6-7), 2008. [3] Schwiedrzik et al., Phil Mag 96 (32-34), 2016

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Structural analysis and Dynamics Properties of Archaeological Wood with

High-Resolution Solid-State 13C NMR

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, 1670-1676. [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.

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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.

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Advances in cellulose dissolution: From scattering and rheology to a new

NMR approach

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.

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Heterogeneous swelling and dissolution of cellulosic fibres in aqueous

solvents: role of cell walls and supramolecular structure

P. Navard1, N. Le Moigne2 1 CEMEF, MINES ParisTech - CNRS UMR 7635, 06904 Sophia Antipolis, France 2 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.

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Absorption in wood: capturing all the effects by MD

D. Derome1, C. Zhang1, J. Carmeliet2

1 EMPA, Applied Wood Materials Laboratory, Dübendorf, Switzerland 2 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.

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High-resolution structure of cellulose to the nanostructure of wood: neutron

/ X-ray scattering and molecular modeling

Y. Nishiyama1, Y. Ogawa1, T. Kuribayashi2 1 CERMAV, CNRS, 38041 Grenoble, France 2 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.

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Development of a new characterization method to analyse Cypermethrin

penetration in wood material by immunolabelling

S. Tapin-Lingua1, K. Ruel2, J.-P. Joseleau2, D. Messaoudi, M. Petit-Conil1 1 FCBA, InTechFibres, Domaine universitaire CS 90251, 38044 Grenoble, France 2 LINK Conseil, 38570 Le Cheylas, France 3 Berkem Développement, 33290 Blanquefort, France 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.

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LIST OF PARTICIPANTS

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BAGLIONI Piero baglioni@csgi.unifit.it

Dept Chimica "Ugo Schiff", Univ Firenze

Firenze Italy

BARDET Michel michel.bardet@cea.fr CEA, INAC Grenoble France

BERG John bergj@ethz.ch ETH Zurich Zurich Switzerland

BERTINETTI Luca luca.bertinetti@mpikg.mpg.de

Max Planck of Colloids and Interfaces

Potsdam Germany

BOSSU Julie julie.bossu@enscm.fr

Institut Charles Gerhardt Montpellier

Montpellier France

BOUDOU Caroline boudou@ill.fr ILL Grenoble France

CAPRON Marie marie.capron@esrf.fr ESRF, PSCM Grenoble France

CHAUMAT Gilles gilles.chaumat@cea.fr ARC-Nucléart, CEA Grenoble France

CRISTIGLIO Viviana cristigl@ill.fr Institut Laue Langevin Grenoble France

DEMÉ Bruno deme@ill.fr Institut Laue-Langevin Grenoble France

DEROME Dominique dominique.derome@empa.ch EMPA Dübendorf Switzerland

DI RENZO Francesco direnzo@enscm.fr Institut Charles Gerhardt Montpellier France

DOLLIÉ Lucas lucas.dollie@lgp2.grenoble-inp.fr LGP2 Saint-Martin-D'hères

France

FROMENT Karine karine.froment@cea.fr ARC-Nucléart Grenoble France

GABRIEL Jean-Christophe

jean-christophe.gabriel@cea.fr CEA Grenoble France

GONZALES Juan Francisco juan.fransisco.gonzales@mah.se Malmö University Malmö Sweden

GRILLO Isabelle grillo@ill.fr Institut Laue Langevin Grenoble France

GRÜNEWALD Tilman tilman.gruenewald@esrf.fr ESRF Grenoble France

GUIZANI Chamseddine guizani.c@gmail.com LGP2 Grenoble Gières France

HESS David hessd@ill.fr Institut Laue Langevin Grenoble France

JOHNSON Mark johnson@ill.eu Institut Laue Langevin Grenoble France

KUNZ Werner Werner.Kunz@chemie.uni-regensburg.de

Institute of Physical and Theoretical Chemistry, University of Regensburg,

Regensburg Germany

LAUTRU Joseph joseph.lautru@cea.fr ICSM Bagnols Sur Cèze Cedex

France

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LECOURT Michael Michael.LECOURT@fcba.fr FCBA Grenoble France

LE MOIGNE Nicolas nicolas.le-moigne@mines-ales.fr Ecole des mines d'Ales Ales France

MADER Alison mader@ill.fr ILL Grenoble France

MEDRONHO Bruno bfmedronho@ualg.pt University of Algarve Faro Portugal

NISHIYAMA Yoshiharu yoshi@cermav.cnrs.fr CNRS Gieres France

PASSAS Raphaël raphael.passas@pagora.grenoble-inp.fr

LGP2 St Martin D'hères

France

PENTTILÄ Paavo penttila@ill.eu Institut Laue-Langevin Grenoble France

PIVA Eleonora eleonora.piva@port.ac.uk Portsmouth University Portsmouth England

PODOR Renaud renaud.podor@cea.fr ICSM Bagnols sur Cèze

France

PONTONI Diego diego.pontoni@esrf.fr ESRF PSCM Grenoble France

PRÉVOST Sylvain prevost@ill.fr Institut Laue Langevin Grenoble France

RENNHOFER Harald harald.rennhofer@boku.ac.at

Institute of Physics and Materials Science, BOKU, Vienna

Vienna Austria

SANDAK Jakub sandak@ivalsa.cnr.it CNR-IVALSA San Michele All'adige

Italy

SCHOFIELD Eleanor e.schofield@maryrose.org Mary Rose Trust Portsmouth England

SCHWEINS Ralf schweins@ill.eu Institut Laue Langevin Grenoble France

SCHWIEDRZIK Jakob jakob.schwiedrzik@empa.ch EMPA Thun Switzerland

SEGMEHL Jana jsegmehl@ethz.ch ETH Zurich Zurich Switzerland

SUSINI Jean jean.susini@esrf.fr ESRF Grenoble France

TAPIN-LINGUA Sandra sandra.tapin-lingua@fcba.fr FCBA Grenoble France

TRAN Khoi quoc-khoi.tran@cea.fr CEA ARC-NUCLEART Grenoble France

ZEMB Thomas thomas.zemb@icsm.fr ICSM Bagnols sur Cèze

France

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