Wood modifications are becoming popular as a way to enhance the performance of wood, either to make it more durable, improve the performance of wood, or give it new functionality as a multifunctional or smart material. While wood modifications have been examined since the early 1900s, the topic has become a dominant area of study in wood science over the past decade. This review summarizes recent advances and provides future perspective on a selection of wood modifications, i.e., the methods that are currently commercialized (acetylation, furfurylation, and thermal modification), a rediscovered ancient practice (charring), a family of polymerization modifications that have so far made it to the pilot scale, and examples of novel wood-based functional materials explored at laboratory scale.

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.

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.

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 (\({\text{d}}M/{\text{d}}t\)) drops below a certain value. However, the errors associated with determining EMC in this manner have never been characterized. Here, an operational definition 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 \({\text{d}}M/{\text{d}}t\) “stop criteria” and the errors in EMC associated with those stop criteria are quantified. 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 \({\text{d}}M/{\text{d}}t\) 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.

Water vapor sorption is the most fundamental aspect of wood-moisture relations. It is directly or indirectly related to the physical properties of wood and the onset of wood-damage mechanisms. While sorption properties of cellulosic materials have been utilized since antiquity, the time-dependent transition from one moisture content to another (i.e., sorption kinetics) has received much less attention. In this critical review, we present the state-of-the-art of water vapor sorption kinetics in wood. We first examine different experimental methods that have been used to measure sorption kinetics, from the quartz helix vacuum balance beginning in earnest in the 1930s, to automated sorption balances used recently. We then give an overview of experimental observations and describe the physical phenomena that occur during the sorption process, which potentially govern the following kinetics: boundary layer mass transfer resistance, heat of sorption, cell wall diffusion, swelling, and polymer mobility. Finally, we evaluate theoretical models that have been proposed for describing sorption kinetics, considering both experimental data and the physical processes described in the previous section. It is clear that no previously developed model can phenomenologically describe the sorption process. Instead, new models are needed. We conclude that the development of new models will require more than simple gravimetric measurements. In addition to mass changes, complementary techniques are needed to probe other important physical quantities on multiple length scales.