Study of chemical modifications and fungi degradation of thermally modified wood using DRIFT spectroscopy

A mild thermal treatment of wood leads to improved macroscopic properties (dimensional stabilization and resistance against fungal degradation). The chemical modifications induced by the thermal treatment were investigated by means of DRIFT spectroscopy on wood blocks in order to explain the new macroscopic properties on a molecular level. The formation of new ether linkage was observed in addition to the well-known acidic hydrolysis reactions of wood. Fungal attack was found to take place even after thermal degradation of pentosanes by a standard oxidative way. A competition between depolymerization and condensation reactions was observed.     

Physical properties of burnt timber, with special focus on the drying performance

Burnt wood has been found to perform different from sound (green) wood when dried together, but also with regards to other physical and mechanical properties. In this study the drying performance of wood burnt to different degrees in recent plantation fires was investigated, and the physical, chemical and wood anatomical properties of these different wood types were determined. Different cell structure and chemical composition due to thermal degradation could be observed as well as different drying performance and variation in mechanical properties. An explanation for the deviant drying performance was attempted with the observed structural changes.     

Development of new wood treatments combining boron impregnation and thermo modification: effect of additives on boron leachability

Environmental pressures in France and in most European countries during the last decade have led to the development of more environmentally acceptable preservation methods. In this context, wood heat treatment is one of the most investigated alternative methods. Important chemical modifications resulting from thermo-degradation reactions confer new properties to wood, like increased decay resistance or higher dimensional stability, while mechanical properties like tensile strength decrease after treatment. However, the improved durability of heat treated wood is not sufficient to allow its utilization in ground contact, where it is subjected to insect and fungi attacks. Impregnation with borax before thermal treatment could be an interesting method to improve the properties of thermally modified wood. Boron is a relatively harmless biocide that improves resistance to fungi and insects like termites. Additionally, borax can also improve wood fire resistance due to its fire retardant effect. To reduce boron leachability, two additives previously developed in the laboratory corresponding to water soluble polymerizable polyglycerol derivatives were added to the borax solution, taking advantage of thermal treatment to fix the latter through polymerization within the wood structure limiting boron leachability.     

Influence of thermo-vacuum treatment on thermal degradation of various wood species

Solid wood has a certain amount of resistance to fire exposure. Recently, there is also great interest in characterization of the thermal behaviour of treated wood due to increasing demand of such products within the perspective of sustainability of environment. The objective of this study was to evaluate and predict the thermal decomposition process of samples from different wood species, Norway spruce (Picea abies Karst.), common ash (Fraxinus excelsior L.) and Turkey oak (Quercus cerris L.), so that such data can be used for enhanced design of wood products for more effective and better utilization in different applications. Spruce and ash samples were treated at a temperature of 190 °C for 2 h while Turkey oak specimens were steamed at a temperature of 110 °C for 24 h before they were thermally treated at a temperature of 160 °C for 3 h. A thermo-gravimetric analysis of the samples highlighted intraspecific differences in mass loss and the stage of thermal degradation between treated and untreated specimens. The degradation of the wood was characterized by twofold reaction stages, with an exception of Norway spruce samples, which exhibited a one-stage reaction. In addition, thermal treatments affected chemical composition of wood. The obtained results will be helpful in determining the applicability of these materials according to their thermal degradation properties.     

Effect of oil type, temperature and time on moisture properties of hot oil-treated wood

This paper focuses on the moisture properties of wood treated in palm oil-, soy oil- and slack wax for different processing times and temperatures. Also, the relative importance of oil uptake and thermal modification on the wood moisture properties is investigated. Slack wax was better than palm oil or soy oil in improving the moisture performance of thermally treated wood, and treatment at 220 °C was superior to treatment at 200 °C, with 4 h being generally better than 2 h treatment. Water absorption in samples treated with wax at 100 °C or 160 °C was similar to that in samples treated at high temperatures while improved anti-shrink efficiencies (ASE) and lower hygroscopicities occurred only for the high temperature treatments. Chloroform extracted samples treated at high temperature with palm oil or soy oil had relatively similar hygroscopicity and ASE properties compared to unextracted samples, but had greatly increased water absorption properties. These results confirm that chemical reactions in wood resulting from the heat treatment account for the main improvements of wood properties in reduced hygroscopicity and improved dimensional stability, while the oil absorbed by wood reduces the rate of water absorption.     

Thermal stability of <Emphasis Type="Italic">Abies alba</Emphasis> wood according to its radial position and forest management

Most of the defects affecting heat-treated wood quality are often attributed to heterogeneous heat transfers in industrial kilns. Even if interspecific variability of wood has been reported to affect thermal degradation of the material, little has been reported on the effects of intraspecific variability. The aim of this work was to study the effect of intraspecific variability of silver fir (Abies alba Mill.) wood on its thermal degradation. For this purpose, wood samples were sampled along the radius of cross-sections to estimate the effect of radial position on wood thermal degradation. Sampling was carried out on discs of four trees, two resulting from dynamic growth stand and two from standard growth stand. The study was performed at different scales: at wood compartments scale involving juvenile and mature heartwood, transition zone between heartwood and sapwood and sapwood as well as at intra-ring scale. Wood samples were ground to sawdust and subjected to thermogravimetric analysis and chemical analysis. Juvenile heartwood was shown to be more sensitive to thermal degradation than other compartments. The thermal behavior of sapwood was not particularly different from that of heartwood, and the presence of extractives did not influence significantly thermal degradation. Earlywood was more sensitive to thermal degradation than latewood explaining the higher susceptibility of fast growing heartwood containing larger rings with higher contents of earlywood.     

Reduction of the surface colour variability of thermally modified <Emphasis Type="Italic">Eucalyptus globulus</Emphasis> wood by colour pre-grading and homogeneity thermal treatment

A new method that consists of combining wood pre-grading by surface colour followed by the application of homogeneity thermal treatments is proposed to reduce the surface colour variability of the thermally modified blue gum wood. To identify the conditions of the homogeneity thermal treatment for two pre-graded groups with different initial surface colours (pinkish and yellowish), the effects of applying 25 different thermal treatment intensities to such groups were analysed. The effects of this method on mass loss and volumetric swelling were also analysed. Results show that an optical pre-grading of the wood samples and treatments under different conditions can reduce the colour variability of the blue gum wood samples, as well as the volumetric swelling. Mass loss was not homogenised after the treatment, but the difference of masses between the two groups was similar to their untreated state. The application of this new methodology may be of interest for the sawn timber industry to bring more uniform boards on the markets and to promote Eucalyptus globulus as a price-competitive and sustainable alternative timber.     

Effect of heat treatment intensity on wood chemical composition and decay durability of Pinus patula

Heat treatment is an effective method to improve biological resistance of low natural durability wood species. The aim of this study was to enhance the decay resistance of Pinus patula, an African low natural durability softwood species, via wood thermal modification technique. Heat treatment was performed on wood specimens under inert conditions at different heat treatment intensities to reach mass losses of 5, 10 and 15%. Heat treated specimens were exposed to fungal decay using the brown rot fungus Poria placenta. The wood chemical and elemental composition was determined as well as extractives toxicity before and after wood thermal modification to understand the reasons of durability improvement. The treated specimens exhibited a significant increase in their durability against wood decay in line with the severity of the treatment. Wood holocellulose was found to be distinctly more sensitive to the heating process than the lignin constituent. In addition, obvious correlations were observed between weight losses recorded after fungal exposure and both holocellulose decrease and lignin ratio increase. The same correlations were observed with the elemental composition changes allowing using the observed differences for predicting of wood durability conferred by heat treatment. Furthermore, no significant differences were observed between the toxicity of Pinus patula wood extractives before and after its thermal modification.     

Effect of ellagitannins,ellagic acid and volatile compounds from oak wood on the (+)‐catechin,procyanidin B1 and malvidin‐3‐glucoside content of model wines

Background and Aims: During ageing in oak barrels, wine undergoes changes because of the release of polyphenols and other molecules from wood. The aim of this study was to evaluate the influence of some oak wood‐derived volatile compounds, ellagic acid and oak wood extracts on the levels of (+)‐catechin, procyanidin B1 and malvidin‐3‐glucoside. Methods and Results: Phenolics and the oak wood derived volatile compounds studied were quantified by HPLC and by GC, respectively. Additionally, the new compounds formed in the solutions were characterised by their spectral properties. Ellagic acid and/or oak wood extracts slowed the decline in the levels of (+)‐catechin and procyanidin B1. In contrast, the decrease in malvidin‐3‐glucoside was more pronounced in the presence of ellagic acid and oak wood chip extracts. Furfural slowed (+)‐catechin degradation, while breakdown of malvidin‐3‐glucoside was slightly more pronounced in the presence of guaiacol, furfural, vanillin and eugenol. (+)‐Catechin, procyanidin B1 and malvidin‐3‐glucoside did not significantly affect the rate of the degradation of ellagitannins during the storage time studied. Finally, new HPLC peaks were detected in the solutions containing (+)‐catechin and ellagic acid, as well as with malvidin‐3‐glucoside with ellagic acid and oak wood extract. Conclusions: Malvidin 3‐glucoside and (+)‐catechin and procyanidin B1 presented distinct behaviours during time in the presence of volatile and non‐volatile compounds from oak wood. Significance of the Study: This work points out the importance of oak wood components in the degradation of anthocyanins and tannins, as well as the reactions that occur during the ageing of red wine.     

Visualising and quantifying thermal degradation of wood by computed tomography

Wood samples from South African pine were subjected to thermal degradation of varying degrees, and their dimensional change as well as changes in cell wall density were determined with a micro CT scanner. It was possible to visualise and quantify those changes and also determine a temperature threshold above which the degradation seemed to be too severe to use this wood for any structural purposes. Below this threshold, however, wood properties changed little and the wood may still be of economic value.     

Influence of temperature of thermal treatment on surface densification of spruce

Spruce (Picea abies L. Karst) wood lamellae, thermally treated at 170, 190, 210 and 230 °C were surface densified by compression at a temperature of 150 °C to three degrees of compression. Immediate springback, set recovery, mechanical properties in 3-point flexure, Brinell hardness and density profiles measurements were used to determine the effect of thermal treatment on the properties of surface densified wood. The highest immediate springback occurred in wood specimens thermally treated at the highest temperature (230 °C) and decreased with decreasing thermal treatment temperature. The untreated samples had the highest set recovery, which decreased with the temperature of thermal treatment. The surface densification increased hardness and bending strength. The highest increase was in the case of untreated wood and decreased with the temperature of thermal treatment. The modulus of elasticity (MOE) and modulus of rupture (MOR) of surface densified wood decreased with increasing thermal treatment temperature. The trend was similar for specimens which were thermally treated but not surface densified. Surface densification increased the density of the specimens in the first few millimetres below the surface. The highest density was achieved in untreated specimens and the lowest in specimens thermally treated at the highest temperature.     

Improvement of the heat treatment of Jack pine (Pinus banksiana) using ThermoWood technology

Thermal treatment in inert atmosphere is used to preserve wood without utilisation of toxic chemical agents. In addition, this process increases the dimensional stability of the wood matrix and results in attractive dark colour. On the other hand, it can deteriorate the mechanical strength and the flexibility of wood. For this reason, heat treatment parameters (such as maximum temperature, heating rate, the duration of the first plateau at constant temperature (100–120°C) and the second plateau at the maximum treatment temperature, humidity, final cool down rate) must be optimised in order to benefit from advantages of thermal treatment without deteriorating significantly the mechanical properties of wood. Correlation between wood properties and thermal treatment parameters depends not only on the wood species but also the environment (climate, soil) where the given species grow. This paper presents a study on thermal treatment of Canadian Jack pine (Pinus banksiana) using a medium size prototype furnace. The aim of this study was to optimize the set of parameters used during industrial treatments. The possibility of shortening the process time without causing any deterioration in wood quality was also investigated. The results show that increasing the maximum heat-treatment temperature increased the dimensional stability of Jack pine and darkened its colour. This parameter did not affect the modulus of elasticity but it decreased the modulus of rupture of Jack pine. A slight reduction in gas humidity during the initial warming up period permitted to shorten the drying period and at the same time increased the mechanical strength. This improvement helps save energy and increase productivity.     

Monosaccharide anhydrides,new markers of toasted oak wood used for ageing wines and distillates

In order to shed light on the thermal carbohydrate transformation chemistry, the non-volatile composition of natural and toasted oak wood samples of different origins were studied. GC–MS analysis revealed the presence of monosaccharide anhydrides (MAs) only in toasted oak wood samples. They were formed by the cellulose and hemicelluloses thermal degradation produced during the toasting process, and the content was dependent on the degree of toasting. The principal MAs formed in the oak wood toasting process were 1,6-anhydro-β-d-glucopyranose (levoglucosan), 1,6-anhydro-β-d-galactosane (galactosan) and 1,6-anhydro-β-d-mannopyranose (mannosan), with levoglucosan being the dominant MAs detected. Monosaccharide anhydrides can be considered specific products formed during the thermal treatment of wood; therefore they are proposed as markers of toasted wood and could be used to monitor and determine the intensity of toasting process.     

Thermal studies of wood impregnated with ZnCl<Subscript>2</Subscript>

In this work the thermal behavior of wood impregnated with ZnCl₂ is studied. Impregnation of wood with ZnCl₂ is a treatment used in activated carbon production, and liquefaction and fast pyrolysis of biomass. Frequently, the impregnated wood is dried for several hours at temperatures above 370 K and then it is carbonized. Catalytic pyrolysis occurs, giving rise to a complex set of reactions. A TG/DTA study was done on the raw material, the activated carbon, the pure ZnCl₂ and the intermediate products in order to study the mass and thermal changes occurring. Elemental analysis and SEM analysis were also carried out. An exothermic torrefaction develops during the drying step; the torrefied product is carbonized in an endothermic process that involves ZnCl₂ volatilization. The washed impregnated wood carbonizes through an exothermic process that may involve the decomposition of cellulose, lignin and the solid product of hemicellulose torrefaction.     

Macroscopic and microscopic monitoring of swelling of beech wood after impregnation with furfuryl alcohol

Wood furfurylation is a modification method that improves several wood properties. Thereby wood is impregnated with a solution of furfuryl alcohol, catalysts and water, in general. The objective of this study was to understand the penetration of furfuryl alcohol into wood. Furthermore, a possible relationship between the substance amount and the swelling behaviour should be determined. To this end microscopic investigations were conducted to describe the temporal process of penetration and swelling. It was found that the swelling coefficients differ at the microscopic and macroscopic level. The microscopic swelling can reach twice the values of macroscopic swelling.     

Effects of high temperature drying in nitrogen atmosphere on mechanical and colour properties of Norway spruce

Heat treatment and drying processes of wood are always accompanied by material changes. These changes are partly caused by oxidative reactions. This study aims to compare high temperature drying in inert gas atmosphere with conventional kiln drying of spruce wood. The mechanical properties as well as colour changes were measured after drying. In general, higher compression strength was observed for samples dried at high temperatures in nitrogen atmosphere. However, tensile and bending strength proved no significant difference. Corresponding to the strength values increased stiffness values were also observed for the compression samples, whereas for tension and bending samples no significant effect was visible. Up to a temperature of approx. 125 °C discolouration is prevented by drying samples in nitrogen atmosphere.     

Influence of ageing on mechanical properties of wood to wood bonding with wheat flour glue

Earlier research into native wheat flour for wood to wood bonding showed excellent bonding properties comparable to synthetic adhesives, but no data about ageing behaviour is available. Short and long term effects on mechanical properties were analysed by lap joint testing and modified DCB-specimens. Results showed no significant reduction in bonding properties, but a trend to lower adhesive strength after 12 months of storage was noticeable. Changes in wheat polymers were observed by means of DSC and FTIR-ATR. Soluble degradation products of starch were analysed by GC-FID after methanolysis and derivatisation. FTIR measurements indicated changes in the structure of starch, but no appreciable alteration of proteins. Investigations by DSC showed increasing crystallinity during 3 months of storage. After 6 months more degradation products were detected. Results indicated that hydrolysis of starch is responsible for a moderate decrease of bonding performance; wheat proteins seem to be less affected.     

Physical,mechanical and biological properties of thermo-mechanically densified and thermally modified timber using the Vacu<Superscript>3</Superscript>-process

Densification and thermal modification change wood properties in different ways depending on the treatment conditions and the wood species. In the presented investigations, densification and thermal modification were applied consecutively. The primary objective of this treatment combination was the compensation of reduced mechanical properties due to the thermal modification by densification. The combined processes were applied to five European wood species: poplar (Populus nigra L.), beech (Fagus sylvatica L.), Norway spruce (Picea abies Karst.), English oak (Quercus robur L.) and European ash (Fraxinus excelsior L.). Depending on the mean density of the species, a thermo-mechanical densification of 43 or 50% was imposed to improve mechanical strength parallel to the grain. Subsequently, the densified material was thermally modified in the so-called Vacu³-process at 230 °C and 20 or 80% vacuum and at 240 °C and 20% vacuum. The thermal modification resulted in changing wood colour, mechanical strength, hardness, dimensional stability and durability. All the wood modification processes were carried out at industrial scale after pre-tests at laboratory scale. The modified material was characterized regarding flexural properties, static and dynamic hardness, structural integrity, abrasion resistance, moisture dynamics, dimensional stability, and durability against white, brown and soft rot fungi. In summary, the test results showed that the consecutive application of thermo-mechanical densification and thermal modification leads to significantly improved durability whilst mechanical properties at least for beech, ash and poplar remained and the material is dimensionally stable.     

Dielectric and ultrasonic properties of rubber wood. Effect of moisture content grain direction and frequency

Dielectric properties of rubber wood have been studied at low and microwave frequencies with different moisture content and grain direction. The ultrasonic properties were studied with pulsed longitudinal waves of frequency 45 kHz, Two anisotropic directions have been considered for this study — parallel and perpendicular to grain. The low frequencies were of 0.01, 0.1, L0, 10 and 100 Hz and microwave frequencies were of 1, 2.45, 6, 8, 10, 14 and 17 GHz. The moisture content affected the dielectric constant and dielectric loss factor both at low and microwave frequencies? The moisture content above 30% showed little influence on dielectric properties whereas it increases linearly from 0 to 30% in both the grain directions at low frequencies. A continuous increase of dielectric properties was obtained with the increase of moisture content at microwave frequencies and the trend becomes concave upward. Dielectric properties increase as the frequencies increase except dielectric loss factor at microwave frequencies where reverse trends were observed. Little change of dielectric loss factor was obtained at frequencies above 6 GHz. The parallel to grain direction showed higher dielectric constant and dielectric loss factor compared to perpendicular to grain direction. This dielectric anisotropy of wood may be attributed due to the microscopic, macroscopic molecular as well as chemical constituents of wood. Ultrasonic properties were also affected considerably by the moisture content and grain direction. The dried wood showed higher ultrasonic velocity and elastic stiffness constant compared to green wood. The parallel to grain direction exhibits higher ultrasonic velocity and elastic stiffness constant than perpendicular to grain.     

Resistance of thermally modified ash (<Emphasis Type="Italic">Fraxinus excelsior</Emphasis> L.) wood under steam pressure against rot fungi,soil-inhabiting micro-organisms and termites

Thermal modification processes have been developed to increase the biological durability and dimensional stability of wood. The aim of this paper was to study the influence of ThermoWood^® treatment intensity on improvement of wood decay resistance against soil-inhabiting micro-organisms, brown/white rots and termite exposures. All of the tests were carried out in the laboratory with two different complementary research materials. The main research material consisted of ash (Fraxinus excelsior L.) wood thermally modified at temperatures of 170, 200, 215 and 228 °C. The reference materials were untreated ash and beech wood for decay resistance tests, untreated ash wood for soil bed tests and untreated ash, beech and pine wood for termite resistance tests. An agar block test was used to determine the resistance to two brown-rot and two white-rot fungi according to CEN/TS 15083-1 directives. Durability against soil-inhabiting micro-organisms was determined following the CEN/TS 15083-2 directives, by measuring the weight loss, modulus of elasticity (MOE) and modulus of rupture (MOR) after incubation periods of 24, 32 and 90 weeks. Finally, Reticulitermes santonensis species was used for determining the termite attack resistance by non-choice screening tests, with a size sample adjustment according to EN 117 standard directives on control samples and on samples which have previously been exposed to soil bed test. Thermal modification increased the biological durability of all samples. However, high thermal modification temperature above 215 °C, represented by a wood mass loss (ML%) due to thermal degradation of 20%, was needed to reach resistance against decay comparable with the durability classes of ‘‘durable’’ or ‘‘very durable’’ in the soil bed test. The brown-rot and white-rot tests gave slightly better durability classes than the soil bed test. Whatever the heat treatment conditions are, thermally modified ash wood was not efficient against termite attack neither before nor after soft rot degradation.