Mathieu Pétrissans

Wettability of Heat-Treated Wood

Summary The aim of this work was to study the wettability and chemical composition of heat-treated wood. Heat treatment was performed at 240°C under inert atmosphere on four European wood species (pine, spruce, beech and poplar). Contact angle measurements before and after treatment indicated a significant increase in wood hydrophobicity. Advancing contact angles of a water drop were in all cases systematically higher for heat-treated than for untreated wood. Chemical modifications of wood after heat treatment were investigated using FTIR and 13C NMR analysis. FTIR spectra indicated little structural change which could be attributed either to carbon-carbon double bond formation or to adsorbed water. NMR spectra also revealed little chemical change except for the degree of cellulose crystallinity which was considerably higher in heat-treated wood and could explain the higher contact angles.

Wettability changes and mass loss during heat treatment of wood

A new product called torrefied or retified wood can be obtained by mild pyrolysis of wood in a temperature range between 200 and 2608C and under inert atmosphere. Such heat-treated wood dramatically reduces its hygroscopicity and improves its dimensional stability and durability. The main drawback of the torrefied wood is its high brittleness. Another property, often mentioned but not well investigated, is its hydrophobic character (Pétrissans et al. 2003). In fact, the heat-treated wood becomes rather hydrophobic, which could cause some severe problems during varnish or paint deposition. The aim of our study was to investigate the wettability changes and the mass loss during heat treatment of wood at different temperatures. A comparison of these two parameters could add valuable information regarding wettability changes and chemical degradation resulting from retification. Heat treatments were carried out in the temperature range of 40 to 2608C. Four European wood species – pine, spruce, beech, and poplar – were studied here. The contact angle values were measured by the Wilhelmy technique. Wood wettability is generally difficult to measure. For example, the heterogeneous and porous character of wood causes the so-called contact angle hysteresis, that is, a distinct difference between the advancing (ua) and the receding (ur) contact angles (Liptáková and Kúdela 1994). Moreover, the wood extractives may also contaminate the probe liquids during measurement (Wålinder and Johansson 2001). This hysteresis effect can also be related to the chemical heterogeneity (Menawat et al. 1984) and/or to the solid roughness (Dettre and Johnson 1964). The Wilhelmy method, chosen for this study, is not a conventional technique for wood contact angle measurement but gives good results on this material (Gardner et al. 1991; Wålinder and Johansson 2001; Wålinder and Ström 2001; Pétrissans et al. 2003).

Limitation of XPS for analysis of wood species containing high amounts of lipophilic extractives

Chemical composition of Norway spruce and pine, two softwood species, has been investigated by X-ray Photoelectron Spectroscopy (XPS). Contrary to results previously obtained with beech wood, which allow to obtain information on bulk chemical composition from surface composition analysis, XPS analysis appears to be unsuitable for the characterisation of Norway spruce and pine wood chemical composition. Indeed, chemical compositions calculated from XPS data differ strongly from those obtained from microanalyses which are in good agreement with theoretical composition described in the literature. XPS analysis of both the softwood surfaces indicated high carbon contents explained by migration of lipophilic extractives to the surface under the influence of the vacuum necessary for XPS analysis. Nonvolatile extractives contained in wood were extracted and deposited on glass plates and analysed. Survey and detailed C1s spectra indicated similar signals to those recorded on wood surfaces. This phenomenon was not observed when samples had been previously extracted before analysis. These results strongly evidenced that extractives present in both species are able to migrate through resin canals from the bulk of the sample to the surface when put into ultra high vacuum. XPS presents, therefore, some limits in the case of the analysis of softwood species containing extractives able to migrate to the surface during analysis. This behaviour, difficult to control, could lead to erroneous interpretations due to extractives enrichment of the surface under the effect of vacuum.

Effect of heat treatment on extracellular enzymatic activities involved in beech wood degradation by Trametes versicolor

Effect of heat treatment on extracellular enzymes involved in wood degradation by Trametes versicolor was investigated. Heat-treated and untreated beech blocks were exposed to T. versicolor on malt-agar medium and extracellular enzymatic activities investigated. A strong ABTS oxidizing activity has been detected during the first stage of colonization in both cases, while cellulase activities are mainly detected in the case of untreated beech wood. Further investigations carried out on holocellulose, isolated using sodium chlorite delignification procedure and subjected to heat treatment or not, indicate that commercially available cellulases and xylanases are able to hydrolyse untreated holocellulose, while heat-treated holocellulose was not affected. All these data suggest that chemical modifications of wood components during heat treatment disturb enzymatic system involved in wood degradation.

Control of wood thermal treatment and its effects on decay resistance: a review

Key messageAn efficient use of thermal treatment of wood requires a depth understanding of the chemical modifications induced. This is a prerequisite to avoid problems of process control, and to provide high quality treated wood with accurately assessed properties to the market. Properties and structural anatomy of thermally modified woods are slightly different than un-processed woods from a same wood species. So it is necessary to create or adapt new analytical methods to control their quality.ContextHeat treatment as a wood modification process is based on chemical degradation of wood polymer by heat transfer. It improves mainly the resistance of wood to decay and provides dimensional stability. These improvements, which come at the expense of a weakening of mechanical properties, have been extensively studied. Since a decade, researches focused mainly on the understanding of wood thermal degradation, on modelling, on quality prediction and quality control.AimsWe aimed at reviewing the recent advances about (i) the analytical methods used to control thermal treatment; (ii) the effects on wood decay resistance and (iii) the advantages and drawbacks of a potential industrial use of wood heating.MethodsWe carried out a literature review of the main industrial methods used to evaluate the conferred wood properties, by thermal treatment. We used papers and reports published between 1970 and 2015, identified in the web of science data base..ResultsApproximately 100 papers mostly published after 2000 were retrieved. They concentrated on: (i) wood mass loss due to thermal degradation determination, (ii) spectroscopic analyses of wood properties, (iii) colour measurements, (iv) chemical composition, (v) non-destructive mechanical assessments and (vi) use of industrial data.ConclusionsOne of most interesting property of heat-treated wood remains its decay resistance. Durability test with modified wood in laboratory are expensive and time-consuming. This review displays data from different analytical methods, such as spectroscopy, thermogravimetry, chemical analyses or mechanical tests that have the potential to be valuable indicators to assess the durability of heat treated wood at industrial scale. However, each method has its limits and drawbacks, such as the required investment for the equipment, reliability and accuracy of the results and ease of use at industrial scale.

Wood thermodegradation: experimental analysis and modeling of mass loss kinetics

Wood heat treatment is an attractive alternative to improve decay resistance of low natural durability of wood species. Decay resistance is strongly correlated to thermal degradation of wood cell wall components. Some recent studies proposed the use of wood mass loss during the heat treatment as a valuable marker to predict final properties of the material (Hakkou et al. 2006, Welzbacher et al. 2007). In this study, heat treatment was carried out in a relatively low temperature (230°C). Mass loss kinetics was studied using equipment, specially conceived to measure sample�s mass during the thermal treatment. Laboratory experiments were performed for heating rates of 1°C min-1. Mathematical model for kinetics of pyrolysis process was used and validated. During the pyrolysis of dry wood samples under inert atmosphere, measurements of temperature distribution and dynamic weight loss were performed. Five different wood species Fagus sylvatica (Beech), Populus nigra (Poplar), Fraxinus excelsior (Ash), Pinus sylvestris (Pine) and Abies pectinata (Silver Fir) were investigated. The unsteady-state mathematical model equations were solved numerically using the commercial package Femlab 2.0. A detailed discussion of the computational model and the solution algorithm is given. The validity of different model assumptions was analyzed. Experimental results were compared with those calculated by the model. Acceptable agreement was achieved.

Effect of extractives on conferred and natural durability of Cupressus lusitanica heartwood

Abstract• Identification of extractives present in Cupressus lusitanica heartwood has been conducted using GC-MS analyses. The chromatogram of toluene/ethanol extracts indicated the presence of large amounts of benzaldehyde and numerous terpenic compounds such as cedrol, agathadiol, epimanool, bornyl acetate, α-cedrene and β-cedrene.• The effect of these extractives on the natural durability of cypress wood was investigated on heart wood blocks exposed to pure culture of Poria placenta before or after solvent extraction. Weight losses revealed severe fungal degradations on the extracted blocks compared to unextracted ones.• Efficiency of heartwood extractives as inhibitors of the growth of Poria placenta on malt/agar test confirms their contribution to cypress natural durability.• Cypress blocks were treated at 240 °C for different times to reach different levels of thermodegradation to evaluate effect of heat treatment on fungal durability. Results indicate that evaporation of volatile extractives during the first few minutes of heat treatment contribute to decreased wood durability, while longer treatment times lead to the expected improvement of durability.• This study suggests that the content of extractives, which may be modified during wood drying or weathering processes, could be the origin of the conflicting data described in the literature concerning cypress natural durability.Résumé• Les extractibles présents dans le duramen de Cupressus lusitanica ont été analysés par GC-MS. Le chromatogramme des extraits obtenus à l’aide d’un mélange toluène/éthanol met en évidence des quantités importantes de benzaldéhyde et de nombreux composés terpéniques comme le cédrol, l’agathadiol, l’épimanool, l’acétate de bornyl, l’α-cédrène et le β-cédrène.• L’effet des extractibles sur la durabilité naturelle du cyprès a été évalué à l’aide d’essais réalisés sur des blocs préalablement extraits ou non puis exposés à Poria placenta. Les pertes de masse mettent en évidence une dégradation importante des échantillons extraits comparativement aux témoins non extraits.• L’efficacité des extractibles comme inhibiteur de croissance de Poria placenta a été évaluée. Les résultats indiquent une forte inhibition du développement fongique.• Des blocs de cyprès ont été traités à 240 °C pendant des temps variables pour atteindre différents niveaux de thermo-dégradation. L’évaporation des extractibles volatils durant la première phase du traitement thermique conduit à une diminution de la durabilité du bois aux agents de pourriture, alors que des traitements plus longs conduisent à l’augmentation de durabilité attendue.• Cette étude suggère que la teneur en extractibles, susceptible de varier suite au séchage ou aux intempéries, peut être à l’origine des observations contradictoires rapportées dans la littérature concernant la durabilité naturelle du cyprès.

Contribution of gums to natural durability of Prosopis africana heartwood

Abstract The exceptional natural durability of Prosopis africana heartwood was investigated to find potential new biocides for wood preservation. Extractions carried out with different solvents indicated high levels of extractives which explained wood durability towards fungal and insects attacks. However, the extractives were not enough to explain the durability. The hydrophobic character of the wood also likely had a significant effect. Contact angle measurements before and after extraction, indicated that extractives have only a minor effect on wood hydrophobicity. Microscopic analysis reveals the presence of high levels of gums filling the wood cell lumens, limiting the penetration of water.

Variations in the natural density of European oak wood affect thermal degradation during thermal modification

Key messageThermogravimetric analysis, performed on small samples of earlywood (EW) or latewood (LW), indicated that earlywood is more susceptible to thermal degradation than latewood. These results suggest a direct relationship between wood density (which depends on the EW/LW ratio and indirectly on silviculture) and the response of wood during thermo-modification processes.ContextOne of the main difficulties in developing thermo-modified wood products at an industrial scale lies in the difficulty of obtaining consistent products with a stable quality (durability, dimensional stability, color). This may be due either to the thermal treatment process itself or to inter- or intra-specific heterogeneity of wood properties.AimsWe investigated the effect of the natural variability of oak wood, particularly in density, on the degree of thermo-degradation during thermal treatments.MethodsX-ray computed tomography was used to assess the effect of initial wood density of oak boards on their thermo-degradation. Intra-ring wood density was estimated using thermogravimetric analysis and micro-densitometry.ResultsX-ray CT did not allow establishment of a clear correlation between initial wood density and mass loss due to thermo-degradation, while thermogravimetric analysis, performed separately on earlywood and latewood samples, revealed a larger susceptibility to thermal degradation of the less dense earlywood samples compared to more dense latewood samplesConclusionInitial wood density, which is directly controlled by the earlywood/latewood ratio modulated by silvicultural practices, directly influences thermo-degradation during thermal treatment. Initial wood density therefore appears to be a potential parameter influencing industrial thermal treatment processes.

Utilization of temperature kinetics as a method to predict treatment intensity and corresponding treated wood quality: Durability and mechanical properties of thermally modified wood

Wood heat treatment is an attractive alternative to improve decay resistance of wood species with low natural durability. However, this improvement of durability is realized at the expense of the mechanical resistance. Decay resistance and mechanical properties are strongly correlated to thermal degradation of wood cells wall components. Mass loss resulting from this degradation is a good indicator of treatment intensity and final treated wood properties. However, the introduction of a fast and accurate system for measuring this mass loss on an industrial scale is very difficult. Nowadays, many studies are conducted on the determination of control parameters which could be correlated with the treatment conditions and final heat treated wood quality such as decay resistance. The aim of this study is to investigate the relations between kinetics of temperature used during thermal treatment process representing heat treatment intensity, mass losses due to thermal degradation and conferred properties to heat treated wood. It might appear that relative area of treatment temperature curves is a good indicator of treatment intensity. Heat treatment with different treatment conditions (temperature-time) have been performed under vacuum, on four wood species (one hardwood and three softwoods) in order to obtain thermal degradation mass loses of 8, 10 and 12%. For each experiment, relative areas corresponding to temperature kinetics, mass loss, decay resistance and mechanical properties have been determined. Results highlight the statement that the temperature curves’ area constitutes a good indicator in the prediction of needed treatment intensity, to obtain required wood durability and mechanical properties such as bending resistance and Brinell hardness.