Wettability and the hysteresis effect in the sorption of water vapor by wood

Summary The hysteresis effect in the adsorption and desorption of water vapor by wood has been variously explained as a consequence of differences in (1) the availability of bonding sites for sorption on molecular surfaces, (2) the degree of aggregation of a swelling or shrinking cellulosic gel system, and (3) the wettability of submicroscopic capillaries within the cell wall.The wettability hysteresis of 28 tropical woods, calculated as the ratio of cosines of advancing and receding contact angles made by water, has been determined by the inclined plate method.For 13 of these species the availability of complete sorption isotherms permitted analysis by means of the Hailwood-Horrobin model to differentiate between monomolecular and polymolecular sorbed moisture. In the upper range of relative humidities, total sorption hysteresis is primarily the result of hysteresis in polymolecular sorption.Positive relationships found in this study between polymolecular sorption hysteresis and wettability hysteresis are consistent with the Kelvin equation with respect to the effect of varying contact angle and give at least partial support to Zsigmondy's explanation of hysteresis as a phenomenon of capillary condensation.Total sorption hysteresis for all 28 species in the upper range of relative humidities was also positively correlated with wettability hysteresis due to the predominant effect of polymolecular sorption hysteresis. It may be concluded that in the range of relative humidity above 60 percent, hysteresis shown by typical sigmoid isotherms is to a considerable degree a phenomenon of capillary condensation explainable by the Kelvin equation in its complete form including cosine of contact angle.

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Zusammenfassung Die Hysterese bei Adsorption und Desorption von Wasserdampf in Holz wird in der Regel als Folge von Unterschieden bei 1. der Zugänglichkeit von Bindungsstellen für die Sorption an molekulare Schichten, 2. des Aggregatzustandes eines quellenden oder schwindenden Cellulose-Gel-Systems und 3. der Benetzbarkeit der submikroskopischen Kapillaren innerhalb der Zellwand erklärt. Die Benetzbarkeits-Hysterese bei 28 tropischen Holzarten wurde durch das Verfahren mit geneigter Ebene bestimmt durch die Berechnung des Verhältnisses der cos-Werte des vorderen und hinteren Kontaktwinkels von Wasser.Bei 13 der geprüften Holzarten erlaubte das Vorhandensein der vollständigen Sorptionsisothermen eine Analyse mit Hilfe des Hailwood-Horrobin-Modells zur Unterscheidung zwischen monomolekular und polymolekular sorbierter Feuchtigkeit. In den höheren Bereichen der relativen Feuchtigkeit ist die Gesamtsorptionshysterese vorwiegend das Ergebnis der polymolekularen Sorption.Die in dieser Untersuchung gefundenen positiven Zusammenhänge zwischen der Hysterese der polymolekularen Sorption und der Benetzungshysterese stehen in Übereinstimmung mit der Kelvinschen Gleichung hinsichtlich des Einflusses des variierenden Kontaktwinkels und sie unterstützen, zumindest teilweise, die Theorie von Zsigmondy über die Hysterese als einer Erscheinung der Kapillar-Kondensation.Im oberen Bereich der relativen Feuchtigkeiten korrelierte die Gesamt-Sorptionshysterese für alle 28 Holzarten ebenfalls positiv mit der Benetzungshysterese infolge des überwiegenden Einflusses der polymolekularen Sorptionshysterese. Hieraus kann geschlossen werden, daß im Bereich der relativen Feuchtigkeit über 60% die Hysterese, die sich in einem typischen S-förmigen Verlauf der Sorptionsisothermen zeigt, zu einem wesentlichen Grade eine Erscheinung der Kapillarkondensation ist und durch die gesamte Kelvin-Gleichung, einschließlich des cos-Kontaktwinkels, erklärt werden kann.

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This research is part of a comprehensive study being conducted at the Yale School of Forestry in cooperation with the Office of Naval Research, U.S. Navy, under Contract No. 609(13), Project NR 330-001, Properties of Tropical Woods.     

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.     

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 effect of openings on combined bound water and water vapor diffusion in wood

This study was undertaken to estimate the effect of openings between cell walls on combined bound water and water vapor diffusion in wood. Using a newly developed model, the radial and tangential moisture diffusion coefficients can be predicted depending on the opening area. The new model explicitly involves a term for water vapor diffusion through the openings, as well as a term for the combined diffusion of bound water and water vapor. A classical model developed by Stamm and Choong had higher longitudinal moisture diffusion coefficients than that in the parallel model at higher moisture content, which is inconsistent with the Wiener bound rule. The new model suggested in this article is useful for analyzing the experimental results and understanding the variability of the diffusion coefficients.     

Short hold times in dynamic vapor sorption measurements mischaracterize the equilibrium moisture content of wood

Recently, the dynamic vapor sorption (DVS) technique has been used to measure sorption isotherms and develop moisture-mechanics models for wood and cellulosic materials. This method typically involves measuring the time-dependent mass response of a sample following step changes in relative humidity (RH), fitting a kinetic model to the data, and extrapolating the asymptotic mass. A series of steps covering the full RH range is used to generate the sorption isotherm. The majority of prior DVS data were taken with hold times of either 60 min or until the change in moisture content was <0.002% per minute over a 10-min period. Here, DVS measurements on wood and isolated wood polymers are presented where the hold times at certain relative humidity steps were much longer, ranging between 24 and 50 h. The data clearly show that the criteria for hold time in previous DVS measurements result in significant errors in prediction of the asymptotic mass. Although the data at short times are consistent with previous measurements, the data exhibit slow sorption behavior with characteristic times on the order of 500–2000 min that cannot be identified with shorter hold times. The results suggest that new hold time criteria need to be developed for dynamic vapor sorption measurements in wood.     

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.     

Statics and kinetics of water vapor sorption of small loblolly pine samples

A better understanding of the sorption behavior of different wood structures could be useful in protecting wood against wood deterioration and fungal attack. The purpose of this study was to investigate the effect of differences among earlywood, latewood, and tree ring location within the stem cross-section of loblolly pine (Pinus taeda) on the sorption kinetics and statics of water vapor under ambient conditions. The water vapor sorption of earlywood and latewood in different tree rings was recorded using a dynamic contact angle analyzer under relative humidity changes from 11 to 89%, as provided by saturated salt solutions. Earlywood had higher sorption rates and diffusion coefficients than latewood, while outer tree rings had higher sorption rates and diffusion coefficients than inner tree rings. The sorption isotherms of earlywood, latewood, and different tree ring locations within the stem cross-section were fitted very well by a Hailwood–Horrobin model.     

Analysis of the temperature dependence of water sorption for wood on the basis of dual mode theory

Isotherm curves of water sorption for wood at various temperatures were analyzed based on the dual mode theory where the total coverage was represented by a linear combination of the Langmuir and Henry equations. The saturation concentration and affinity constant of the Langmuir equation and the parameter of Henry’s law had a transition point near 60°C. The analysis based on the dual mode theory found that the constants for whole wood were related to those of wood components and depended more on their glass transition temperatures. That is, it was theoretically demonstrated that the characteristic tem-perature dependence of water sorption for wood occurs because wood consists of three components (cellulose, hemicellulose, and lignin) with different glass transition temperatures.     

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).     

磁化浸种促进林木种子发芽生长的初步研究

用不同磁场和不同磁场强度处理的水对林木种子浸种培育，观察种子发芽率、发芽势、胚根和下胚轴的变化。实验结果表明，磁化水能提高林木种子的发芽率、发芽势，促进幼苗的生长；匀场比梯度场好，磁场强度为0.4T的比0.2T的好。但对不同的树种其影响程度有所不同。     

Wood in the stationary state: Zero entropy gradients for water vapor and bound water

Summary According to nonequilibrium thermodynamics, the local rate of entropy production is minimized for moist wood in the stationary state. Furthermore, the rate of entropy production due to moisture flow must be zero in this state. Conservation of energy applied to the steady flow of water vapor through an arbitrarily selected volume element of wood shows that the vapor entropy gradient is zero. Because the entropy production due to moisture flow must be balanced by a corresponding entropy flow away from the element, entropy gradients for bound water and water vapor are equal and the bound water entropy gradient also is zero.     

机械循环热水采暖系统常见故障及防治

分析机械循环热水采暖系统常见故障,为解决实际问题提供防治方法     

Variation of measured cross-sectional cell dimensions and calculated water vapor permeability across a single growth ring of spruce wood

A statistical study of the cell dimensions in a growth ring of spruce along the radial and tangential directions is performed. The data are used to study the variation of the cell vapor permeability in the growth ring. Studying cell rows within one growth ring, the frequency distributions of the cell wall thickness in the radial direction and of the lumen dimension in the tangential direction are found to be both unimodal. In contrast, the frequency distributions of these dimensions in the other directions are bimodal, where the different modes can be attributed to earlywood and latewood. Analysis of the bimodal distributions results in the determination of threshold values of cell wall thickness and the lumen dimension for earlywood and latewood tracheids. The cell dimensions are used to predict cell porosity and water vapor permeability distribution within a growth ring. The bimodal frequency distributions of the tangential cell wall thickness and the radial lumen dimension provide an explanation for the observed bimodal frequency distribution of the cell water vapor permeability both in radial and in tangential directions. Contrary to measured macroscopic vapor permeability results, the tracheid geometry results in lower cell vapor permeability in radial than in tangential direction. This confirms that rays play an important role in the vapor permeability of wood, as they can be considered as pathways for vapor transport in radial direction. The dataset analyzed in this paper leads to a set of parameters characterizing the earlywood and latewood cell dimensions. Such characterization can be used, for example, for producing synthetic data for computational modeling studies.     

Influence of wood planing on the second-order effects of moisture sorption in sugar maple

Summary Two types of machines, a conventional planer, and a fixed-knife pressure-bar planer were used to prepare matched specimens of sugar maple wood. After adsorption and desorption, both experiments at 21 °C, the EMC, swelling in all principal directions as well as compliance coefficient in radial compression were measured. Two specimen sizes were used for these expe‐riments. For a given equilibrium moisture content, tangential and radial dimensions were greater after desorption than after adsorption, as previously described. When equilibrium was reached by gaining moisture, the wood was stiffer in radial compression compared to when the equilibrium was reached after losing moisture. The magnitude of this phenomenon, second-order effects of moisture sorption, was slightly affected by the type of planing. These effects on swelling were greater for large specimens prepared by conventional planing compared to fixed-knife pressure-bar planing. Small specimens showed similar magnitudes of this phenomenon with both planing methods. No differences between planing methods were found for the radial compliance coefficient measured on either specimen size. Therefore, the second-order effects of moisture sorption appeared to be a bulk phenomenon and not restricted to the superficial layers of wood. Received 9 December 1997     

Mechano-sorptive creep mechanism of wood in compression and bending

Summary A model is introduced which links the mechano-sorptive behaviour of wood subjected to moderate and high compression or bending stresses parallel to grain to the formation of slip planes in the cell wall. Slip plane formation is dependent on the breaking of hydrogen bonds, which process is directly related to the amount of moisture change. The dramatic change of microfibril orientation in slip plane zones cause an increase of the longitudinal shrinkage/swelling and a decrease of the modulus of elasticity. These features of slip plane formation account for both the magnitude and the oscillation of the excessive mechano-sorptive creep associated with compression and bending parallel to grain. A summary is given of the characteristics of the mechano-sorptive effects, and the model is discussed in the light of these effects.The paper is one of the results of a project on the influence of changing moisture content on the mechanical behavior of wood, currently underway in a co-operation between College of Environmental Science and Forestry, State University of New York, and the Technical University of Denmark. Support for this project is provided by the Danish Technical Research Council and by the USDA C--operative Research Program (proj. 85-FSTY-9-0112). The support is gratefully acknowledged