Acetylated wood (W_Ac) shows improved properties largely due to the reduced amount of water in its cell wall, but the exact mechanism of water reduction remains unclear. Acetylation reduces hydroxyl (OH) content by acetyl (Ac) substitution but may also limit water access to unmodified OH groups by steric hindrance. In the present work, the accessibility of OH groups in acetylated or propionylated Radiata pine (Pinus radiata D. Don) wood (W_Ac and W_Pr) was investigated by deuterium exchange, saponification in sodium hydroxide followed by high-performance liquid chromatography (HPLC) analysis and weight percentage gain determination of the modified samples. Acetylation reduced OH accessibility (OH_A) to a greater extent than would be predicted, if OH substitution were the only responsible mechanism for accessibility reduction. The combination of deuterium exchange and saponification results provides strong evidence that steric hindrance plays a key role in reduction of water accessibility to unmodified OH groups in W_Ac. The supramolecular architecture of W_Pr samples seems to be modified by the propionylation reaction, which leads to increased OH_A at low levels of substitution. This suggests that molecular restructuring within the cell wall exposes new OH groups after propionylation. At higher levels of substitution, however, the W_Pr exhibited less OH_A than expected indicating steric hindrance from the propionyl groups.

The effect of wood modification on wood-water interactions in modified wood is poorly understood, even though water is a critical factor in fungal wood degradation. A previous review suggested that decay resistance in modified wood is caused by a reduced wood moisture content (MC) that inhibits the diffusion of oxidative fungal metabolites. It has been reported that a MC below 23%–25% will protect wood from decay, which correlates with the weight percent gain (WPG) level seen to inhibit decay in modified wood for several different kinds of wood modifications. In this review, the focus is on the role of water in brown rot decay of chemically and thermally modified wood. The study synthesizes recent advances in the inhibition of decay and the effects of wood modification on the MC and moisture relationships in modified wood. We discuss three potential mechanisms for diffusion inhibition in modified wood: (i) nanopore blocking; (ii) capillary condensation in nanopores; and (iii) plasticization of hemicelluloses. The nanopore blocking theory works well with cell wall bulking and crosslinking modifications, but it seems less applicable to thermal modification, which may increase nanoporosity. Preventing the formation of capillary water in nanopores also explains cell wall bulking modification well. However, the possibility of increased nanoporosity in thermally modified wood and increased wood-water surface tension for 1.3-dimethylol-4.5-dihydroxyethyleneurea (DMDHEU) modification complicate the interpretation of this theory for these modifications. Inhibition of hemicellulose plasticization fits well with diffusion prevention in acetylated, DMDHEU and thermally modified wood, but plasticity in furfurylated wood may be increased. We also point out that the different mechanisms are not mutually exclusive, and it may be the case that they all play some role to varying degrees for each modification. Furthermore, we highlight recent work which shows that brown rot fungi will eventually degrade modified wood materials, even at high treatment levels. The herein reviewed literature suggests that the modification itself may initially be degraded, followed by an increase in wood cell wall MC to a level where chemical transport is possible.

Moisture in radiata pine (Pinus radiataD. Don) earlywood (EW), which was acetylated or propionylated to various degrees, was measured by low-field nuclear magnetic resonance (LFNMR) relaxometry. Spin-spin relaxation times (T₂) were determined for fully saturated samples at 22 and −18°C.T₂values for EW lumen water increased with increasing acetylation weight percentage gain (WPG), perhaps caused by the less hydrophilic acetylated wood (AcW) surface. Cell wall water (W_CW) and the water in pits and small voids also showed increasingT₂values as a function of WPG but with a weaker tendency. A possible explanation is the counteracting effects of decreased hydrophilicity and reduced moisture content (MC) of these water populations at higher levels of acetylation. The evaluation of propionylation on W_CWT₂data was complicated by peak splitting in the relaxation spectrum. ConstantT₂values for void water populations at various WPG levels for propionylated samples indicate a modification gradient in the cell wall. Fiber saturation point (FSP) was significantly reduced by both modifications. Slightly higher FSP values for propionylated samples suggest that physical bulking is not the only factor causing moisture exclusion in AcW. But this interpretation is tentative because of the possibility of cell wall damage caused by propionylation.

Research Highlights: Polyesterification of wood with sorbitol and citric acid (SCA) increases decay resistance against brown-rot and white-rot fungi without reducing cell wall moisture content but the SCA polymer is susceptible to hydrolysis. Background and Objectives: SCA polyesterification is a low-cost, bio-based chemical wood modification system with potential for commercialisation. Materials and Methods: This study investigates moisture-related properties and decay resistance in SCA-modified wood. Scots pine sapwood was polyesterified at 140 °C with various SCA solution concentrations ranging from 14–56% w/w. Dimensional stability was assessed and leachates were analysed with high-performance liquid chromatography (HPLC). Chemical changes were characterized with attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) and spectra were quantitatively compared with peak ratios. Low-field nuclear magnetic resonance (LFNMR) relaxometry was used to assess water saturated samples and decay resistance was determined with a modified EN113 test. Results: Anti-swelling efficiency (ASE) ranged from 23–43% and decreased at higher weight percentage gains (WPG). Reduced ASE at higher WPG resulted from increased water saturated volumes for higher treatment levels. HPLC analysis of leachates showed detectable citric acid levels even after an EN84 leaching procedure. ATR-FTIR analysis indicated increased ester content in the SCA-modified samples and decreased hydroxyl content compared to controls. Cell wall water assessed by non-freezing moisture content determined with LFNMR was found to increase because of the modification. SCA-modified samples resisted brown-rot and white-rot decay, with a potential decay threshold of 50% WPG. Sterile reference samples incubated without fungi revealed substantial mass loss due to leaching of the samples in a high humidity environment. The susceptibility of the SCA polymer to hydrolysis was confirmed by analysing the sorption behaviour of the pure polymer in a dynamic vapour sorption apparatus. Conclusions: SCA wood modification is an effective means for imparting decay resistance but, using the curing parameters in the current study, prolonged low-level leaching due to hydrolysis of the SCA polymer remains a problem.

The material properties of wood are intimately tied to the amount of moisture contained in the wood cell walls. The moisture content depends on the environmental conditions, i.e. temperature and relative humidity, but also on material characteristics of the wood itself. The exact mechanisms governing moisture equilibrium between wood cell walls and environmental conditions remain obscure, likely because multiple material characteristics have been proposed to be involved. In this study, we used a data exploration approach to illuminate the important wood characteristics determining the cell wall moisture content in the full moisture range. Specimens of nine different wood species (two softwoods and seven hardwoods) were examined in terms of their material characteristics at multiple scales and their cell wall moisture content was measured in equilibrium with both hygroscopic conditions and at water-saturation. By statistical analysis, the chemical composition was found to be the most important predictor of the cell wall moisture content in the full moisture range. For the other wood characteristics the importance differed between the low moisture range and the humid and saturated conditions. In the low moisture range, the cellulose crystallinity and hydroxyl accessibility were found to be important predictors, while at high moisture contents the microfibril orientation in the S1 and S3 layers of the cell walls was important. Overall, the results highlighted that no single wood characteristic were decisive for the cell wall moisture content, and each of the predictors identified by the analysis had only a small effect in themselves on the cell wall moisture content. Wood characteristics with a major effect on the cell wall moisture content were, therefore, not identified..

Wood is a porous, hygroscopic material with engineering properties that depend significantly on the amount of water (moisture) in the material. Water in wood can be present in both cell walls and the porous void-structure of the material, but it is only water in cell walls that affects the engineering properties. An important characteristic of wood is therefore the capacity for water of its solid cell walls, i.e. the maximum cell wall moisture content. However, this quantity is not straight-forward to determine experimentally, and the measured value may depend on the experimental technique used. In this study, we used a triangulation approach to determine the maximum cell wall moisture content by using three experimental techniques based on different measurement principles: low-field nuclear magnetic resonance (LFNMR) relaxometry, differential scanning calorimetry (DSC), and the solute exclusion technique (SET). The LFNMR data were furthermore analysed by two varieties of exponential decay analysis. These techniques were used to determine the maximum cell wall moisture contents of nine different wood species, covering a wide range of densities. The results from statistical analysis showed that LFNMR yielded lower cell wall moisture contents than DSC and SET, which were fairly similar. Both of the latter methods include factors that could either under-estimate or over-estimate the measured cell wall moisture content. Because of this and the fact that the DSC and SET methods are based on different measurement principles, it is likely that they provide realistic values of the cell wall moisture content in the water-saturated state.