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Despite the importance of cell wall diffusion to nearly all aspects of wood utilization, diffusion mechanisms and the detailed effects of moisture remain poorly understood. In this perspective, we introduce and employ approaches established in polymer science to develop a phenomenological framework for understanding the effects of moisture on diffusion in unmodified wood cell walls. The premise for applying this polymer-science-based approach to wood is that wood polymers (cellulose, hemicelluloses, and lignin) behave like typical solid polymers. Therefore, the movement of chemicals through wood cell walls is a diffusion process through a solid polymer, which is in contrast to previous assertions that transport of some chemicals occurs via aqueous pathways in the cell wall layers. Diffusion in polymers depends on the interrelations between free volume in the polymer matrix, molecular motions of the polymer, diffusant dimensions, and solubility of the diffusant in the polymer matrix. Because diffusion strongly depends on whether a polymer is in a rigid glassy state or soft rubbery state, it is important to understand glass transitions in the amorphous wood polymers. Through a review and analysis of available literature, we conclude that in wood both lignin and the amorphous polysaccharides very likely have glass transitions. After developing and presenting this polymer-science-based perspective of diffusion through unmodified wood cell walls, suggested directions for future research are discussed. A key consideration is that a large difference between diffusion through wood polymers and typical polymers is the high swelling pressures that can develop in unmodified wood cell walls. This pressure likely arises from the hierarchical structure of wood and should be taken into consideration in the development of predictive models for diffusion in unmodified wood cell walls.

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Dynamic vapor sorption (DVS) measurements are widely used to collect water vapor sorption isotherms for wood and other cellulosic materials. Equilibrium moisture content (EMC) is typically assumed to have been reached when the rate of change in moisture content with time (dM∕dt) drops below a certain value. However, the errors associated with determining EMC in this manner have never been characterized. Here, an operational defnition of equilibrium for DVS measurements is provided, and twenty test cases over four cellulosic materials are presented where the relative humidity was stepped up or down and then held constant until equilibrium was reached. Then, both the time to reach various dM∕dt "stop criteria" and the errors in EMC associated with those stop criteria are quantifed. The errors in the EMC from the widely used 0.002% min −1 stop criterion are found to be as large as 1.2% MC, and the average error for 20 test cases is 0.5% MC, which are much larger than the 0.1% MC error claimed in the literature. Longer data collection times are recommended, and a more stringent dM∕dt criterion (0.0003% min −1 , using a 2-h window) for cellulosic materials is proposed. The errors with this criterion are less than 0.75% MC, and the average error is 0.3% MC. Furthermore, it is shown that the errors for a given stop criterion are systematic and can be fairly well characterized with a simple linear regression. Finally, a correction for systematic error is proposed that results in more accurate EMC values with shorter hold times.

Diffusion of chemicals and ions through the wood cell wall plays an important role in wood damage mechanisms. In the present work, free diffusion of ions through wood secondary walls and middle lamellae has been investigated as a function of moisture content (MC) and anatomical direction. Various ions (K, Cl, Zn, Cu) were injected into selected regions of 2 μm thick wood sections with a microinjector and then the ion distribution was mapped by means of X-ray fluorescence microscopy with submicron spatial resolution. The MC of the wood was controlled in situ by means of climatic chamber with controlled relative humidity (RH). For all ions investigated, there was a threshold RH below which the concentration profiles did not change. The threshold RH depended upon ionic species, cell wall layer, and wood anatomical orientation. Above the threshold RH, differences in mobility among ions were observed and the mobility depended upon anatomical direction and cell wall layer. These observations support a recently proposed percolation model of electrical conduction in wood. The results contribute to understanding the mechanisms of fungal decay and fastener corrosion that occur below the fiber saturation point.

Chemical modification of wood increases decay resistance but the exact mechanisms remain poorly understood. Recently, Ringman and coauthors examined established theories addressing why modified wood has increased decay resistance and concluded that the most probable cause of inhibition and/or delay of initiation of brown-rot decay is lowering the equilibrium moisture content. In another recent study, Jakes and coauthors examined moisture-induced wood damage mechanisms, including decay and fastener corrosion, and observed that these mechanisms require chemical transport through wood cell walls. They proposed that chemical transport within wood cell walls is controlled by a moisture-induced glass transition in interconnected networks of hemicelluloses and amorphous cellulose. This paper shows how these models jointly suggest mechanisms by which wood modifications can inhibit brown-rot. Alternative mechanisms are also discussed. These models can be used to understand and further improve the performance of wood modification systems.

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Our future bioeconomy depends on increased utilization of renewable lignocellulosic biomass. Controlling the diffusion of chemicals, such as inorganic ions, within secondary plant cell walls is central to many biomass applications. However, insufficient understanding of intra-cell-wall diffusion within secondary plant cell walls is hindering the advancement of many lignocellulosic biomass applications. In this work, X-ray fluorescence microscopy was used to measure diffusion constants of K + , cu 2+ , and Cl − diffusing through loblolly pine (Pinus taeda) cell wall layers under 70%, 75%, or 80% relative humidity (RH). Results revealed that diffusion constants increased with RH, the larger Cu 2+ diffused more slowly than the K + , and the Cl − diffusion constant was the same as that for the counter cation, indicating cations and anions diffused together to maintain charge neutrality. Comparison with electrical conductivity measurements showed that conductivity is being controlled by ion mobility over these RH. The results further support that intra-cell-wall diffusion of inorganic ions is a Fickian diffusion process occurring through rubbery amorphous polysaccharides, which contradicts previous assertions that intra-cell-wall diffusion is an aqueous process occurring through water pathways. Researchers can now utilize polymer science approaches to engineer the molecular architecture of lignocellulosic biomass to optimize properties for specific end uses.