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This study aimed at a better understanding of the wood-water interaction, in particular the role of the hydroxyl accessibility during the humidity-dependent change in moisture content. Thin sections (80 µm) of never-dried Norway spruce sapwood that contained early- and latewood were used for the experiments. Sorption isotherm measurements confirmed the humidity-dependent moisture content changes and the effect of the first drying of the wood sections. Changes in hydroxyl accessibility were then determined by deuteration of the sections using deuterium oxide, followed by their re-protonation in water (H2O) vapor at different relative humidity: 15, 55 or 95%. The deuteration and re-protonation of the wood sections were quantified by dry mass changes as well as by changes in the OH and OD stretching vibrations in the Fourier transform infrared spectra. The results showed that the deuterated sections could be almost completely re-protonated in H2O vapor, nearly irrespective of the applied relative humidity. Therefore, changes in hydroxyl accessibility were not the driving force for the humidity-dependent changes in moisture content. However, a slow re-protonation rate at low relative humidity had to be considered. Nonetheless, a small quantity of OD groups persisted the re-protonation in H2O vapor and liquid H2O, which was not related to the drying of the wood. [ABSTRACT FROM AUTHOR]

The objective of the study was to investigate the water vapour sorption behaviour of thermally modified (TM) wood powder, e.g. ground wood prepared from waste streams of TM solid wood, and wood powder that was extracted in pressurised hot water. Solid spruce wood was TM in steam conditions (210°C for 3 h), milled and hot-water-extracted (HWE) at elevated pressure (140°C for 1 h). The results evidence that the hot-water extraction reduced the water sorption and the accessible hydroxyl group concentration by the removal of amorphous carbohydrates. In contrast, the enhanced cross-linking of the cell wall matrix and the annealing of amorphous matrix polymers during thermal modification reduced the sorption behaviour of wood additionally, without further reducing the hydroxyl accessibility. These additional effects of thermal modification were at least partially cancelled by hot-water extraction. The results bring novel insights into the mechanisms that reduce the water vapour sorption of wood by compositional and structural changes induced by heating. [ABSTRACT FROM AUTHOR]

Acetylated wood (WAc) 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 (WAc and WPr) was investigated by deuterium exchange, saponification in sodium hydroxide followed by highperformance liquid chromatography (HPLC) analysis and weight percentage gain determination of the modified samples. Acetylation reduced OH accessibility (OHA) 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 WAc. The supramolecular architecture of WPr samples seems to be modified by the propionylation reaction, which leads to increased OHA 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 WPr exhibited less OHA than expected indicating steric hindrance from the propionyl groups. [ABSTRACT FROM AUTHOR]

The first drying of wood cell walls from the native state has sometimes been described as producing irreversible structural changes which reduce the accessibility to water, a phenomenon often referred to as hornification. This study demonstrates that while changes do seem to take place, these are more complex than what has hitherto been described. The accessibility of wood cell wall hydroxyls to deuteration in the form of liquid water was not found to be affected by drying, since vacuum impregnation with liquid water restores the native cell wall accessibility. Contrary to this, hydroxyl accessibility to deuteration by water vapour was found to decrease to different levels depending on the drying conditions. Vacuum drying at 60 °C for 3 days reduced the accessibility more than drying for 1 day at 103 °C without vacuum. Drying for 3 days at 103 °C increased the hydroxyl accessibility compared to 1 day. Moreover, the decrease in hydroxyl accessibility to deuteration by water vapour induced by the first drying could be at least partially erased by subsequent vacuum impregnation with liquid water, indicating reversibility. For the drying of solid, non-degraded wood cell walls the results challenge the often supposed process of hornification, understood as a permanent decrease in hydroxyl accessibility to water. [ABSTRACT FROM AUTHOR]