Wood-water interactions are central to the utilization of wood in our society since water affects many important characteristics of wood. This topic has been investigated for more than a century, but new knowledge continues to be generated as a result of improved experimental and computational methods. This review summarizes our current understanding of the fundamentals of water in wood and highlights significant knowledge gaps. Thus, the focus is not only on what is currently known but equally important, what is yet unknown. The review covers locations of water in wood; phase changes and equilibrium states of water in wood; thermodynamics of sorption; terminology including cell wall water (bound water), capillary water (free water), fiber saturation point, and maximum cell wall moisture content; shrinkage and swelling; sorption hysteresis; transport of water in wood; and kinetics of water vapor sorption in the cell wall.

Moisture plays a central role in the performance of wood products because it affects important material properties such as the resistance to decomposition, the mechanical properties, and the dimensions. To improve wood performance, a wide range of wood modification techniques that alter the wood chemistry in various ways have been described in the literature. Typically, these modifications aim to improve resistance to decomposition, dimensional stability, or, to introduce novel functionalities in the wood. However, wood modification techniques can also be an important tool to improve our understanding of the interactions between wood and moisture. In this review, we describe current knowledge gaps in our understanding of moisture in wood and how modification has been and could be used to clarify some of these gaps. This review shows that introducing specific chemical changes, and even controlling the distribution of these, in combination with the variety of experimental methods available for characterization of moisture in wood, could give novel insights into the interaction between moisture and wood. Such insights could further contribute to applications in several related fields of research such as how to enhance the resistance to decomposition, how to improve the performance of moisture-induced wooden actuators, or how to improve the utilization of wood biomass with challenging swelling anisotropy.

Sorption isotherms describe the relation between the equilibrium moisture content of a material and the ambient relative humidity. Most materials exhibits

Wood is a hygroscopic material that absorbs and desorbs water to equilibrate to the ambient climate. Within material science, the moisture range from 0 to about 95–98% relative humidity is generally called the hygroscopic moisture range, while the exceeding moisture range is called the over-hygroscopic moisture range. For wood, the dominating mechanisms of moisture sorption are different in these two moisture ranges; in the hygroscopic range, water is primarily bound by hydrogen bonding in cell walls, and, in the over-hygroscopic range, water uptake mainly occurs via capillary condensation outside cell walls in macro voids such as cell lumina and pit chambers. Since large volumes of water can be taken up here, the moisture content in the over-hygroscopic range increases extensively in a very narrow relative humidity range. The over-hygroscopic range is particularly relevant for durability applications since fungal degradation occurs primarily in this moisture range. This review describes the mechanisms behind moisture sorption in the over-hygroscopic moisture range, methods that can be used to study the interactions between wood and water at these high humidity levels, and the current state of knowledge on interactions between modified wood and water. A lack of studies on interactions between modified wood and water in the over-hygroscopic range was identified, and the possibility of combining different methods to acquire information on amount, state, and location of water in modified wood at several well-defined high moisture states was pointed out. Since water potential is an important parameter for fungal growth, such studies could possibly give important clues concerning the mechanisms behind the increased resistance to degradation obtained by wood modification.

Low-field nuclear magnetic resonance (LFNMR) relaxometry was applied to determine the spin-spin relaxation time (T ₂) of water-saturated Norway spruce (Picea abies (L.) Karst.) specimens cut from mature sapwood (sW) and mature and juvenile heartwood (hW), where earlywood (EW) and latewood (LW) were separated. In combination with quantitative wood anatomy data focusing on the void volumes in various morphological regions, the NMR data served for a more reliable assignment of free-water populations found in water-saturated solid wood. Two free-water populations were identified within most sample types. One was assigned to water in the tracheid lumen and the other to water inside bordered pits. Whether water in the ray cell lumina was included in one or the other of these two populations depends on the curve-fit method applied (continuous or discrete). In addition, T ₂ differences between the different tissue types were studied and, for comparison, sorption isotherms were measured by means of a sorption balance. There was a significant difference between EW and LW as well as between juvenile wood and mature wood in terms of T ₂ related to the cell wall water. However, no differences were seen between the sorption isotherms, which indicates that the observed T ₂ differences were not due to differences in cell wall moisture content (MC).

Moisture influences most physical wood properties and plays an important role in degradation processes. Like most other porous materials, wood exhibits sorption hysteresis. That is, the moisture content is higher if equilibrium is reached by desorption than if it is reached by absorption under the same ambient climate conditions. The mechanism of moisture uptake by wood are different in the hygroscopic and over-hygroscopic moisture ranges and due to methodical issues, most studies of sorption hysteresis have been performed in the hygroscopic range. In the present study, total sorption hysteresis was separated into hysteresis in cell wall water and capillary water respectively in the whole moisture range by a novel combination of experimental techniques. Wood specimens were conditioned to several high moisture contents using a new system based on the pressure plate technique, and the distinction between cell wall water and capillary water was done with differential scanning calorimetry. The results showed that sorption hysteresis in wood cell walls exists in the whole moisture range. The cell walls were not saturated with water until the whole wood specimen was saturated which contradicts the long-held dogma that cell walls are saturated before significant amounts of capillary water are present in wood.