Dynamic water vapour sorption properties of wood treated with glutaraldehyde

The dynamic water vapour sorption properties of Scots pine (Pinus sylvestris L.) wood samples were studied to investigate the modifying effects of glutaraldehyde. Pine sapwood was treated with solutions of glutaraldehyde and a catalyst (magnesium chloride) to obtain weight per cent gains of 0.5, 8.6, 15.5, and 21.0%, respectively. The sorption behaviour of untreated and treated wood was measured using a Dynamic Vapour Sorption apparatus. The results showed considerable reduction in equilibrium moisture content of wood and the corresponding equilibrium time at each target relative humidity (RH) due to glutaraldehyde treatment. The moisture adsorption and desorption rates of modified and unmodified wood were generally faster in the low RH range (up to approximate 20%) than in the high range. Modification primarily reduced the adsorption and desorption rates over the high RH range of 20–95%. Glutaraldehyde modification resulted in a reduction in sorption hysteresis due to the loss of elasticity of cell walls.     

The influence of curing conditions on the chemical distribution in wood modified with thermosetting resins

Scots pine (Pinus sylvestris L.) sapwood was impregnated with aqueous solutions of phenol formaldehyde and methylated melamine formaldehyde resins and subsequently cured in an oven. One set of specimens was cured in plastic bags to avoid drying (wet curing) while another set of samples was heated and water was allowed to freely evaporate (dry curing). Macroscopic resin distribution was investigated using X-ray densitometry and infrared spectroscopy (FTIR-ATR). During dry curing, the resins migrated to the wood surface resulting in a gradient. Wet curing resulted in even distribution of the resins because it was immobilized due to condensation and precipitation in the wood. Neither densitometry nor FTIR-ATR was found to be generally applicable for investigating resin distribution in modified wood. Wet curing resulted in low cell wall bulking as compared to dry curing, probably because resin precipitated before drying. Storing impregnated wood prior to curing under non-drying conditions (“diffusion phase”) also reduced cell wall penetration and bulking.     

Measurements of water vapour sorption in wood

Summary Results from sorption measurements at 23 °C on Picea abies in the intervals 54 to 75% RH and 75 to 84% RH are reported. In the higher interval non-Fickian sorption is clearly seen.This work was supported by the Swedish Building Research Council     

The sorption of water vapour of wood treated with a nanotechnology compound

The potential of improving the hygroscopicity of solid wood by applying a new nanotechnology compound was investigated. The sorption isotherms were analysed using the Hailwood–Horrobin model. The experimental analysis of the sorption isotherms showed that the treatment affected total, polymolecular and monomolecular sorption. The application of the compound reduced the total sorption by 26.5%, polymolecular sorption by 23.9% and monomolecular sorption by 33.1% at saturation.     

The sorption of water vapour by anhydride modified softwood

A comprehensive investigation into the effect of molecular size of the substituent group of softwood modified with linear chain carboxylic acid anhydrides, namely acetic, propionic, butyric, valeric, hexanoic, upon the sorption of water vapour has been performed. The sorption isotherms for untreated and chemically modified wood were analysed using the Hailwood–Horrobin model. The experimental analysis of the sorption isotherms showed that esterification affects the total, polymolecular and monomolecular sorption. The effect of molecular size of the substituent group on site accessibility was addressed by comparing the effect on water vapour sorption produced by adducts with differences in molecular size. Similar levels of cell-wall bulking were produced at different levels of hydroxyl substitution. Analysis of the sorption isotherms at comparable weight percentage gain revealed that the five anhydrides used show similar effectiveness in both total, polymolecular and monomolecular sorption, despite the substantial difference in the proportion of hydroxyl groups reacted. It is concluded that the reduction in total, polymolecular and monomolecular sorption produced by the linear chain anhydrides is primarily determined by the volume of adduct deposited in the cell wall (bulking) rather than by the number of hydroxyl groups that have been substituted. The validity of the Hailwood–Horrobin model is questioned.     

Water vapour diffusion through historically relevant glutin-based wood adhesives with sorption measurements and neutron radiography

In this work, the sorption and moisture diffusion behaviour of historically relevant glutin-based adhesives (i.e. bone glue, hide glue, fish glue) is characterized. The adhesive’s sorption isotherms were assessed on thin film samples revealing fundamental differences between the glutin-based adhesives and the synthetic reference adhesive (polyurethane). Furthermore, the water vapour diffusion parallel to the fibre was examined by means of neutron imaging on bonded two-layer samples of Norway spruce wood. In contrast to previous studies using neutron imaging, a new evaluation approach is presented, which allows for nonzero initial moisture conditions and takes into account and compensates for the geometry changes in the sample caused by swelling and shrinkage, thus allowing for a characterization of the diffusion behaviour within the glue line. The diffusion coefficients determined with neutron imaging were interpreted in terms of a theoretical model which takes into account the glue line microstructure. Although the diffusion coefficients were on average larger values for the glutin-based adhesives compared to the reference polyurethane adhesive, the significant variation observed in the sorption measurement is not reflected. This can partially be ascribed to excessive penetration of the adhesives into the wood substrate in fibre direction, which impedes a continuous adhesive layer. Furthermore, deformation and densification of the wood structure was assessed in the vicinity of the adhesive joint. This effect can be ascribed to the surface roughness, which results in very high local stresses leading to buckling and deformation of the tracheids. This situation is similar to that found for adhesive joints in or close to the fibre direction such as finger or butt joints.     

The sorption of water vapour by chemically modified softwood: analysis using various sorption models

The sorption data for Corsican pine wood chemically modified with a homologous series of linear chain carboxylic acid anhydrides was analysed using various models, namely, BET, Dent, Le and Ly, Hailwood and Horrobin, Nelson, and Henderson. Hailwood and Horrobin resulted in the more appropriate model to represent the equilibrium data of chemically modified wood. In the present study, the parameter representing the molecular weight of the dry cell wall in the Hailwood and Horrobin isotherm was perfectly correlated with the weight percentage gain of anhydride. A linear relation was proposed between these two parameters in order to fit all experimental isotherms (the results showed an r²=0.993).     

Analysis of the water vapour sorption isotherms of thermally modified acacia and sesendok

Abstract

Two Malaysian hardwoods, acacia (Acacia mangium) and sesendok (Endospermum malaccense), that had been subjected to oleo-thermal modification were studied to determine their sorption isotherm behaviour using a dynamic vapour sorption apparatus. All the specimens were thermally modified using palm oil at three different temperatures (180, 200 and 220°C) and three different times (1, 2 and 3 h). The results showed that there was a reduction in equilibrium moisture content at each target relative humidity due to the heat treatment, but that the two wood species showed different behaviour in this respect. The adsorption isotherms were analysed using the Hailwood and Horrobin model, with excellent fits to the experimental data. The monolayer water and polylayer water were both reduced at a range of relative humidity values of the treated samples, although behaviour between the two wood species differed. Heat treatment resulted in an increase in hysteresis ratio, which was probably due to the increase in matrix stiffness of the cell walls.     

Studies on holocellulose and alpha-cellulose from spruce wood using cryo-ultramicrotomy

Summary Cryo-ultramicrotomy was applied to holocellulose and alpha-cellulose from spruce wood (Picea abies Karst.) for a light and electron microscopical study of the removal of lignin during chlorite delignification and the changes in swelling during delignification and alkali extraction. The swelling state of the fibre walls during each stage of treatment was well preserved, and distinct differences could be observed. Staining with uranyl acetate brought out the fine structure of the fibre walls down to the range of elementary fibrils.Submitted by Deutsche Forschungsgemeinschaft. The assistance of Dr. D. Grosser at the light microscope and of Miss U. Schwarz with the chemical analysis is greatly appreciated.     

A multi-species comparison of delta13C from whole wood, extractive-free wood and holocellulose

The stable carbon (C) isotope composition (delta13C) of tree rings is a powerful metric for reconstructing past physiological responses to climate variation. However, accurate measurement and interpretation are complicated by diagenesis and the translocation of compounds with distinct isotopic signatures. Isolation and analysis of cellulose minimizes these complications by eliminating variation due to biosynthetic pathways; however, isolation of cellulose is time-consuming and has no clear endpoint. A faster and better-defined analytical method is desirable. Our objectives were to determine if there is a direct relationship between the isotopic compositions of whole wood (WW), whole wood treated with solvents to remove mobile extractives (extractive-free wood; EF) and holocellulose (HC) isolated by extractive removal and subsequent bleaching. We also determined if total C concentration could explain the isotopic composition and variation among these three wood components of each sample. A set of wood samples of diverse phylogeny, anatomy and chemical composition, was examined. The mean offset or difference between HC and EF delta13C was 1.07 +/- 0.09 per thousand and the offset between HC and WW was 1.32 +/- 0.10 per thousand. Equivalence tests (with alpha = 0.05) indicated that the relationship between EF delta13C and HC delta13C had a slope significantly similar to 1 +/- 5.5%, whereas for the WW delta13C: HC delta13C relationship, the slope was significantly similar to 1 +/- 10.08%. A regression model using EF delta13C to predict HC delta13C had a slope of 0.97, which was not significantly different from unity (P = 0.264), whereas the regression for WW had a slope of 0.92 which was significantly different from unity (P = 0.0098). Carbon concentration was correlated with HC:WW offset and cellulose:EF offset (P = 0.0501 and 0.007, respectively), but neither relationship explained much of the variation (r2 = 0.12 and 0.14, respectively). We suggest that HC extraction is unnecessary for most analyses of tree-ring delta13C; a simple solvent extraction is a suitable alternative for many applications.     

The water vapour sorption properties of Sitka spruce determined using a dynamic vapour sorption apparatus

The water vapour sorption properties of Sitka spruce (Picea abies) have been investigated over a range of temperatures (14.2–43.8°C) using a dynamic vapour sorption apparatus. The sorption kinetics behaviour was evaluated using the parallel exponential kinetics model which has been found to give very accurate fits to the data in studies of foodstuffs or plant fibres, but has not been previously applied to sorption studies with wood. Both the adsorption and desorption kinetics curve can be deconvoluted into a fast and slow exponential process. Under conditions of adsorption, the fast process appears to be associated with the formation of monolayer water (determined using the Hailwood Horrobin model) up to a relative humidity of 20%. Under desorption, there is no clear differentiation between fast and slow processes. The area bounded by the sorption hysteresis loop reduced as the temperature at which the isotherm was measured increased, due to movement of the desorption curve only, with the adsorption curve remaining the same at all temperatures. This behaviour is consistent with sorption processes taking place on nanoporous glassy solids below the glass transition temperature. The heat of wetting was determined from the temperature dependence of the desorption isotherms by using the Clausius–Clapeyron equation, yielding results that are consistent with literature values. However, doubts are raised in this paper as to the applicability of using the Clausius–Clapeyron equation for analyses of this type.     

迪芬巴赫浸渍纸贴面板生产线的特点

迪芬巴赫贴面板生产线是由德国生产的、当今世界最先进的设备之一 ,整条生产线采用了PLC可编程控制 ,厚度检测、铺装、热压等关键工序性能独特 ,优级品率达 99.1%。     

Quantifying lignin and holocellulose content in coniferous decayed wood using near-infrared reflectance spectroscopy

To determine the independent decomposition rates of lignin and cellulose of decayed woody debris, a technique for the rapid analysis of lignin and cellulose is required. We applied a near-infrared spectroscopy (NIRS) technique to measure the lignin and holocellulose content in decayed wood. We succeeded in creating partial least-squares (PLS) models to estimate the lignin and holocellulose content in the decayed wood of five species using NIR spectra. Although the accuracy was acceptable for the estimation of a five-species mixed model (R ² = 0.970 for lignin and R ² = 0.962 for holocellulose), it was further improved when the model was applied to each species independently. This combination of NIRS and a PLS model is a valuable tool for the determination of the lignin and holocellulose content in decayed wood. The technique is time efficient (3 min per sample) and non-hazardous (no acid treatment is required).     

Changes of chemical properties and the water vapour sorption of <Emphasis Type="Italic">Eucalyptus pellita</Emphasis> wood thermally modified in vacuum

The aim of this study was to evaluate the chemical composition and the dynamic water vapour sorption properties of Eucalyptus pellita wood thermally modified in vacuum. For this purpose, wood samples were thermally modified in a vacuum oven at 160–240 °C for 4 h. Chemical composition were investigated by wet chemical analysis, elemental analysis, as well as Fourier transform infrared (FTIR) analysis, and dynamic water vapour sorption properties were evaluated by dynamic vapour sorption apparatus. The results showed that holocellulose and alpha-cellulose contents decreased and lignin and extractives contents relatively increased during the heat process. Elemental analysis showed a reduction in hydrogen content and an increase in carbon content. FTIR analysis indicated that the degradation of hemicellulose and condensation reactions of lignin occurred. In addition, the thermo-vacuum resulted in a reduction in the equilibrium moisture content of wood during the adsorption or desorption process. And the sorption hysteresis had a decreasing trend with increasing treatment temperature. The development of the hygroscopicity was related to the increase in the relative content of lignin, the degradation of the carbonyl groups in xylan and the loss of carbonyl group linked to the aromatic skeleton in lignin after heat treatment.     

Ammonia sorption isotherms of wood and cotton cellulose

Summary Sorption isotherms of ammonia were measured on cellulosic materials, such as beech and birch wood, as well as on cotton cellulose, the object being to obtain information on the nature of interaction between the wood and the ammonia by means of application of various sorption theories. As a result several analogies between the sorption of ammonia vapour and water vapour could be observed.—The isotherms displayed the typical S-shape and developed a hysteresis along the adsorption and desorption lines. The sorbate films reached a thickness of 4–6 molecular layers. The lowering of enthalpy of the ammonia vapour appeared to be the propelling force of the sorption process, as in the case with the uptake of water vapour.—In contrast to water isotherms, however, ammonia isotherms cannot be reproduced with the same specimen. Each sorption cycle brought a loss of substance and a reduction of the fibre saturation capacities of the adsorbent. In ammonia vapour the fibre saturation points were found at sorbate concentrations twice as high as in water vapour. The hysteresis between the adsorption and desorption processes also appeared with ammonia vapour; however, the continuous changes of the adsorbent, caused by chemical interaction with ammonia, produced heavy displacements. The specific surface area of the samples in ammonia was approximately twice the size of that in water, but the extensions varied greatly during the sorption cycles.These investigations have been supported by the Zentenarfonds of the Swiss Federal Institute of Technology.     

Modeling of the sorption hysteresis for wood

This paper deals with an adsorption/desorption model in order to predict evolutions of boundary conditions during the mass transfer process versus time in timber elements. This model is derived from a thermodynamic balance between the free water and its saturated vapor pressure, and is generalized for the bound water phase. It allows describing a realistic adsorption and desorption phenomena characterized by a moisture content hysteresis induced by cyclic variations of the relative humidity and the temperature. The sorption isotherm explains the equilibrium between the bound water phase in wood and the vapor pressure in the environment. The model includes different latent heats for the adsorption and desorption process. An analytic explanation allows to model partial variations in terms of relative humidity domain.     

Laminar sorption and swelling theory for wood and cellulose

Summary The known requirements for the sorption and swelling of wood are reviewed. These are shown to be compatible, in the case of softwoods, with the following simplified model. The fibers are continuous with either rectangular or circular cross sections and lumen of the same shape with a constant size. The fiber walls consist of concentric lamina made up of small repeating units 100 Å by 100 Å, consisting of a microcrystalline core surrounded by an amorphous sheath. All sorption and swelling occurs at the surfaces of or within the amorphous sheath. The major portion of the sorption and swelling is inter-laminar with just sufficient intra-laminar sorption and swelling to avoid laminar distortion. Calculations give the generally accepted internal sorption surface for water of about 200 square meters per gram. The portion of the total sorption that is intra-laminar varies from 5 ... 20 percent in going from wood with a specific gravity of 0.3 ... 1.0. Thickness of sorption in water molecules per sorption site vary from 6.1 ... 4.9 for inter-laminar sorption and 0.35 ... 1.35 for intra-laminar sorption in going from wood with a specific gravity of 0.3 to one of 1.0. Similar values are obtained from experimental swelling data where lumen cross sections change. Similar calculations for super swelling of wood and pulps show that laminar separations may become sufficiently great to be microscopically visible. The calculations show that bound water fiber saturation points for wood normally fall in the range of 25 ... 40 percent. Super swollen wood, chemically isolated fibers and beaten fibers may as a result of reduced restraints have fiber saturation points greater than 150 percent. The latter are attributed to dispersion or diffusion forces rather than the conventional bound water forces of hydrogen bonding for intact wood.

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Zusammenfassung Die bekannten Bedingungen für die Sorption und Quellung von Holz werden erörtert. Sie sind auf Nadelholz unter Anwendung des folgenden, vereinfachten Modells anwendbar. Die Fasern sind durchgehend und haben rechteckigen oder kreisförmigen Querschnitt, mit Zellhohlräumen gleicher Form und konstanter Größe. Die Faserwände bestehen aus konzentrisch angeordneten Schichten, die wiederum aus kleinen, sich wiederholenden 100 ×100 großen Einheiten zusammengesetzt sind; diese wiederum bestehen aus einem mikrokristallinen Kern, umgeben von einer amorphen Auflagerung. Alle Sorptions- und Quellungsvorgänge finden an der Oberfläche oder innerhalb dieser amorphen Auflagerung statt; sie spielen sich in der Hauptsache in der Schicht selbst ab (inter-laminar), jedoch findet genügend Zwischenschicht-Sorption und-Quellung (intra-laminar) statt, um Verformungen der Schichten zu vermeiden. Durch Berechnung erhält man die allgemein anerkannte Größe der inneren Sorptionsfläche für Wasser von etwa 200 m²/g. Der Anteil der intra-laminaren Sorption an der Gesamtsorption schwankt zwischen 5 und 20% bei Holz mit Rohdichten von 0.3 bis 1.0. Die Schichtdicke der sorbierten Wassermoleküle je Sorptionsstelle liegt für inter-laminare Sorption zwischen 6.1 und 4.9, und für intra-laminare Sorption zwischen 0.35 und 1.35 bei Holz mit Rohdichten zwischen 0.3 bis 1.0. Ähnliche Werte ergaben sich aus experimentell ermittelten Quellungsdaten bei Zellhohlräumen mit sich änderndem Querschnitt. Vergleichbare Berechnungen der Super-Quellung des Holzes und des Zellstoffes zeigen, daß laminare Abtrennungen so groß werden können, daß sie mikroskopisch sichtbar werden. Sie zeigen ferner, daß die Fasersättigungspunkte bei gebundenem Wasser meist zwischen 25 und 40% liegen. Extrem gequollenes Holz, chemisch herausgelöste und gemahlene Fasern können aufgrund verringerter Behinderung Fasersättigungspunkte über 150% erreichen. Diese letztere Erscheinung ist eher den Dispersions- oder Diffusionskräften zuzuschreiben als den Kräften aus Wasserstoffbrücken des gebundenen Wassers im intakten Holz.

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Paper No. 2743 of the Journal Series of the N. C. State University Agricultural Experiment Station, Raleigh, North Carolina.

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Anselme Payen award paper of the Cellulose, Wood and Fiber Div., Am. Chem. Soc. presented at their 156th National Meeting in Atlantic City, New Jersey, September, 1968.     

Water sorption mechanisms of commercial wood adhesive films

As water moves inside the wood, the gluelines might act as barriers that are potentially leading to local moistening. Even low amounts of water may influence the mechanical performance of glued wood products. Dynamic vapor sorption analysis was performed to assess the sorption processes of six commercial wood adhesives. Vapor sorption isotherms were compared with vapor uptake dynamics. Phenol–resorcinol–formaldehyde showed high moisture uptake of 18 %, while vapor diffusion speed was low. Fish glue showed a water uptake of 45 % at otherwise moderate vapor uptake speed. Melamine–formaldehyde resin gained 22 % water, and polyvinyl acetate absorbed 10 %. The latter was also the fastest vapor absorbing adhesive. Polyurethane only absorbed 3.5 % of moisture at medium uptake speed. Mechanisms of water diffusion seem to be driven by (1) the available free volume in the polymer and (2) the interacting ionic groups of the polymer chain. While the free volume could be linked to the accumulated moisture, the ionic group interaction might determine the measured vapor diffusion dynamics.     

Fractal dimension of wood surfaces from sorption isotherms

Summary In this paper the method of fractal dimension is applied to characterize the wood surface by using water-sorption data. Three different methods are implemented to determine the fractal dimension. These methods are based on polymolecular sorption and capillary condensation and are found to estimate the fractal dimension in the range of 2.5–2.8. This implies that the estimation of the surface area of wood by determining the number of molecules of water corresponding to monolayer formation is not true. The surface in fact is far from two dimensional as being closer to a three dimensional one.