Volume 75, Issue 4

“Non-Fickian” diffusion of wood moisture refers to the unexplained anomalous behaviour of water vapour sorption in wood. The depression of moisture diffusion rates in thin sections of wood tissue during moisture content change at high relative humidity is one of the least-understood aspects of “non-Fickian” diffusion. In a previous work, a rate-limiting effect by two cooperative couplings of moisture and heat transfer, was shown to generate some signature features of “non-Fickian” diffusion. The present work aims to heuristically study the simultaneous action of this thermal rate-limiting effect and intrinsic slow relaxation processes in wood. Using an analytical non-geometrical model, exact solutions are obtained which show that the thermal rate-limiting effect acts directly and equally on diffusion and all relaxation processes, effectively time-stretching the entire dynamic wood moisture response. The magnitude of the time-scaling effect is proportional to the coupling strength between heat and mass transfer, which increases progressively with the relative humidity.

This article aims at providing a synthetic view of the equilibrium moisture content (EMC) dependence of wood vibrational properties (i.e. dynamic mechanical properties in the audio-frequency range), including specific dynamic modulus of elasticity ( E′ / γ ) and damping coefficient expressing internal friction (tan δ ). A series of multi-trajectories experiments was designed to complete an analytical review. Literature indicates that: (1) in longitudinal (L) direction, the EMC dependence of E′ / γ shows a very consistent shape (rather linear) between studies, while its shape is non-linear for tan δ and varies significantly between studies; (2) EMC dependence of tan δ is rather well documented in the L direction, in adsorption, for softwoods, but data covering EMC dependence in both L and other anisotropic directions, and sorption hysteresis, are still scarce. Experiments were conducted on a softwood (spruce) and a hardwood (maple), in L and radial (R) directions, in full adsorption from oven-dry state, full desorption from water-saturated state, and relative humidity (RH) loops without extreme conditioning. Measurements were made at conditions considered “at equilibrium” and some were monitored through time. Results indicated that tan δ was much more (×3) sensitive to EMC differences than E′ / γ . R properties, especially tan δ R , were much more (×2–3) sensitive than L properties – resulting in strong increase of anisotropy with increasing EMC. In L direction, differences due to EMC remained moderate compared to the natural variability of wood for E′ / γ , while for tan δ the EMC-induced changes were at least equal to natural variability in high-grade spruce. Vibrational properties did exhibit a hysteresis as a function of RH, but very little hysteresis as a function of EMC. The tan δ -EMC relation strongly depended on the actual time of stabilisation after reaching EMC. A related paper will address the transient, out of equilibrium effects of changing moisture conditions on the vibrational properties of wood.

Moisture changes cause transient effects in various polymeric materials. In wood, they are mainly documented in semi-static or low-frequency domains and could explain various anomalies in wood behaviour, including the so-called mechano-sorptive effect. This article aimed at exploring and quantifying transient effects in wood vibrational properties, evidenced but in few publications. A series of 65 experiments on spruce and maple, in longitudinal (L) and radial (R) directions, spanning many humidity trajectories, were monitored through time (1–7 weeks) after step-change in relative humidity (RH). Changes in dimensions and specific dynamic modulus of elasticity ( E′ / γ ) closely followed change in moisture content (MC). But the damping coefficient (tan δ ) always increased (whether MC increased or decreased ) within first hours/days, before slowly re-decreasing. This was quantitatively analysed by subtracting equilibrium moisture content (EMC) dependence from the global changes in tan δ , which simultaneously expressed destabilisation, followed by physical ageing (a slow process towards approaching equilibrium). For small EMC steps, the amplitude of destabilisation in L tan δ exceeded changes due to EMC dependence. Destabilisation was of similar importance relative to L or to R tan δ , while R tan δ showed much (2−4×) stronger EMC dependence. Amplitude of destabilisation increased with wider RH/EMC-steps (and faster sorption rates). Within an experiment, maximum destabilisation occurred nearly concomitantly with maximum sorption rate. Equilibrium was usually reached in MC, even within one week, but seldom in tan δ , even after several weeks. Results suggested that: (i) drying caused similar amplitudes of destabilisation, but that occurred sooner, and recovered faster, than humidifying; (ii) small RH-steps caused relatively smaller amplitudes of destabilisation, but that occurred later, and spanned over longer time before recovering equilibrium, than wide RH-steps. Some possible hypotheses are introduced to explain the observed phenomena. These phenomena also have important practical consequences in real-life wood uses and, particularly, in the design of experimental protocols.

The objective of this work was to provide a rapid and nondestructive imaging method for evaluating the hygroscopic behavior of thermally modified lignocellulosic materials (softwood and hardwood). The difference in the hygroscopic behavior was explained by moisture content (MC) mapping results and molecular association characteristics of absorbed water (i.e. weakly, moderately, and strongly hydrogen-bonded water molecules) with wood at various relative humidities (RH). To achieve this goal, near-infrared (NIR) spectral images in the wavelength range 1816–2130 nm (covering the combination of stretching and deformation vibrations for OH) were used to visualize MC distributions over the surface of Japanese cedar and European beech samples which had been thermally treated at different temperatures. A curve fitting method was utilized to explore changes in water-wood structure characteristics based on shifts to longer wavelength in spectral signals caused by increasing MC. The curve fitting results support the recent nuclear magnetic resonance (NMR) studies that different bound water stabilities may pool in different compartments of the wood cell wall. Furthermore, water was firmly bound to wood at low RHs and H-bonds gained mobility as the number of absorbed molecules increased. It is concluded that NIR hyperspectral imaging also has the potential to be a complementary methodology for studying the transient changes of wood-water interactions before equilibrium.

In this study, the effect of thermo-mechanical densification on the density, hardness, compression strength, bending strength (MOR), and modulus of elasticity (MOE) of fir and aspen wood pretreated with water repellents was analyzed. Wood specimens were impregnated with paraffin, linseed oil and styrene after pre-vacuum treatment. Then, the impregnated wood specimens were densified with compression ratios of 20 and 40%, and at 120, 150 and 180 °C. The results indicated that the density, hardness and strength properties of the all densified specimens (untreated and impregnated) increased depending on the compression ratio and temperature. For all tested properties, higher increases were obtained in the paraffin and styrene pretreated specimens compared to untreated samples. However, the increase rates in linseed oil pretreated specimens were generally lower than untreated specimens. Regarding water repellents the most successful results in all tested properties were determined in styrene pretreated specimens. The density, hardness and strength properties of all specimens increased with the increase in compression ratio. On the other hand, the increase in the compression temperature negatively affects the properties of untreated and linseed oil pretreated specimens, while having a generally positive effect on the properties of paraffin pretreated specimens. However, all tested properties of styrene pretreated specimens have increased significantly due to the increase in compression temperature. The increasing strength properties of wood as a result of densification have increased much more with paraffin and especially styrene pretreatment. These combinations can be considered as an important potential for applications that require more hardness and strength.

The effect of fungicidal components in wood has been known for ages, yet there is no method to assess the impact of such components on the durability of a wood species, as compared to other material characteristics that influence decay. In this paper, the importance of fungicidal effects on the natural durability of 10 wood species is assessed in relation to other decay-influencing factors with a new test, the so-called ‘paste test’. By comparing results from this test with the ‘mini-block test’, on both heartwood and leached sapwood, insight is gained into the significance of fungicidal components on the one hand and other material characteristics on the other hand. The durability of species such as Prunus avium was attributed mainly to fungicidal components. For species such as Pterocarpus soyauxii, durability seemed to be an effect of both fungicidal components and moisture-regulating components, while the latter seemed to be of main importance in regulating the decay of Aucoumea klaineana and Entandrophragma cylindricum . Wood-anatomical features, such as the parenchyma content (in case of brown rot fungi) and the vessel-fiber ratio, possibly affect degradation as well. This work shows that fungicidal components are not always of major importance for the durability of a wood species. The authors hereby emphasize the importance of moisture-regulating components and wood anatomy on the durability of wood.

The conformation of lignin in solvents is major key factors governing the physicochemical properties of aromatic polymers. However, the conformational changes of lignin in good and poor solvents is not clearly understood at the molecular level. In this study, short- (DP 2.77) and long-chain (DP 4.49) lignin oligomer model compounds composed solely of interunit β– O –4 bonds with a narrow polydispersity were synthesized, and their NMR spectra were recorded to evaluate the molecular structural changes induced by addition of water to an organic solvent. The spectral signals were completely assigned in DMSO- d 6 and D 2 O by applying 2D 1 H– 13 C HSQC, HMBC, and long-range heteronuclear single quantum multiple bond correlation (LR-HSQMBC). The conformation of the long- and short-chain lignin models were analyzed by 2D 1 H– 1 H ROESY. In all the solvent systems, consisting of DMSO- d 6 and containing 0–90% volume of acetic acid- d 4 buffer in D 2 O (pD 5.0), the lignin models were found to have folded conformations, but more compact structures were observed in D 2 O compared with DMSO- d 6 .

To improve the reactivity of lignin for incorporation into high value polymers, the introduction of amines via Mannich reaction is a commonly used strategy. During this functionalization reaction, intra- as well as intermolecular lignin–lignin crosslinking occurs, which can vastly change the elastic properties of the lignin, and therefore, the properties of the resulting polymer. Therefore, the molecular structure of the amine that is used for such a lignin functionalization may be of great importance. However, the relationship between the molecular structure of the amine and the elastic properties of the lignin-based polymer that is generated thereof, has not been fully understood. Herein, this relationship was investigated in detail and it was observed that the molecular flexibility of the amines plays a predominant role: The use of more flexible amines results in an increase in elasticity and the use of less flexible amines yields more rigid resin material. In addition to the macroscopic 3-point bending flexural tests, the elastic modules of the resins were determined on the nanometer scale by using atomic force microscopy (AFM) in the PeakForce tapping modus. Thus, it could be demonstrated that the intrinsic elasticities of the lignin domains are the main reason for the observed tendency.

An efficient separation technology for hydrolysates towards a full valorization of bamboo is still a tough challenge, especially regarding the lignin and lignin-carbohydrate complexes (LCCs). The present study aimed to develop a facile approach using organic solvent extraction for efficiently fractionating the main components of bamboo hydrolysates. The high-purity lignin with only a trace of carbohydrates was first obtained by precipitation of the bamboo hydrolysate. The water-soluble lignin (WSL) fraction was extracted in organic solvent through a three-stage organic solvent extraction process, and the hemicellulosic sugars with increased purity were also collected. Furthermore, a thorough characterization including various NMR techniques ( 31 P, 13 C, and 2D-HSQC), GPC, and GC-MS was conducted to the obtained lignin-rich-fractions. It was found that the WSL fraction contained abundant functional groups and tremendous amount of LCC structures. As compared to native LCC of bamboo, the WSL fraction exhibited more typical LCC linkages, i.e. phenyl glycoside linkage, which is the main type of chemical linkage between lignin and carbohydrate in both LCC samples. The results demonstrate that organic phase extraction is a highly efficient protocol for the fractionation of hydrolysate and the isolation of LCC-rich streams possessing great potential applications.