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21 pages, 2374 KiB

Open AccessArticle

Measuring the Heat of Interaction between Lignocellulosic Materials and Water

by Martin Nopens, Lars Wadsö, Christian Ortmann, Michael Fröba and Andreas Krause

Forests 2019, 10(8), 674; https://doi.org/10.3390/f10080674 - 9 Aug 2019

Cited by 18 | Viewed by 3354

Abstract

Research Highlights: When investigating the sorption of water on lignocellulosic materials, the sorption or mixing enthalpy is an interesting parameter that, together with the sorption isotherms commonly measured, can be used to characterize and understand the sorption process. We have compared different [...] Read more.

Research Highlights: When investigating the sorption of water on lignocellulosic materials, the sorption or mixing enthalpy is an interesting parameter that, together with the sorption isotherms commonly measured, can be used to characterize and understand the sorption process. We have compared different methods to assess these enthalpies. Additionally, we propose a sorption nomenclature. Background and Objectives: Sorption enthalpies are non-trivial to measure. We have, for the first time, measured sorption enthalpies on the same materials with four different methods, to be able to compare the method’s strengths and weaknesses. Materials and Methods: The following four methods were used on beech and Scots pine wood: isosteric heat, solution calorimetry, sorption calorimetry, and RH perfusion calorimetry. Results: The results for beech and pine were similar, and were in general agreement with the literature. We do not recommend one of the methods over the others, as they are quite different, and they can therefore be used to elucidate different aspects of the interactions between water and, for example, novel biobased materials (modified woods, cellulose derivatives, and regenerated cellulose). Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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27 pages, 5580 KiB

Open AccessArticle

Wood–Moisture Relationships Studied with Molecular Simulations: Methodological Guidelines

by Mingyang Chen, Chi Zhang, Ali Shomali, Benoit Coasne, Jan Carmeliet and Dominique Derome

Forests 2019, 10(8), 628; https://doi.org/10.3390/f10080628 - 26 Jul 2019

Cited by 22 | Viewed by 5599

Abstract

This paper aims at providing a methodological framework for investigating wood polymers using atomistic modeling, namely, molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations. Atomistic simulations are used to mimic water adsorption and desorption in amorphous polymers, make observations on swelling, [...] Read more.

This paper aims at providing a methodological framework for investigating wood polymers using atomistic modeling, namely, molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations. Atomistic simulations are used to mimic water adsorption and desorption in amorphous polymers, make observations on swelling, mechanical softening, and on hysteresis. This hygromechanical behavior, as observed in particular from the breaking and reforming of hydrogen bonds, is related to the behavior of more complex polymeric composites. Wood is a hierarchical material, where the origin of wood-moisture relationships lies at the nanoporous material scale. As water molecules are adsorbed into the hydrophilic matrix in the cell walls, the induced fluid–solid interaction forces result in swelling of these cell walls. The interaction of the composite polymeric material, that is the layer S2 of the wood cell wall, with water is known to rearrange its internal material structure, which makes it moisture sensitive, influencing its physical properties. In-depth studies of the coupled effects of water sorption on hygric and mechanical properties of different polymeric components can be performed with atomistic modeling. The paper covers the main components of knowledge and good practice for such simulations. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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Review

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16 pages, 1644 KiB

Open AccessReview

On Wood–Water Interactions in the Over-Hygroscopic Moisture Range—Mechanisms, Methods, and Influence of Wood Modification

by Maria Fredriksson

Forests 2019, 10(9), 779; https://doi.org/10.3390/f10090779 - 8 Sep 2019

Cited by 49 | Viewed by 6344

Abstract

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 [...] Read more.

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. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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26 pages, 3504 KiB

Open AccessReview

Kinetics of Water Vapor Sorption in Wood Cell Walls: State of the Art and Research Needs

by Emil Engelund Thybring, Samuel V. Glass and Samuel L. Zelinka

Forests 2019, 10(8), 704; https://doi.org/10.3390/f10080704 - 20 Aug 2019

Cited by 47 | Viewed by 6113

Abstract

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 [...] Read more.

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. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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22 pages, 920 KiB

Open AccessReview

The Importance of Moisture for Brown Rot Degradation of Modified Wood: A Critical Discussion

by Rebecka Ringman, Greeley Beck and Annica Pilgård

Forests 2019, 10(6), 522; https://doi.org/10.3390/f10060522 - 23 Jun 2019

Cited by 48 | Viewed by 5918

Abstract

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 [...] Read more.

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. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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Other

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48 pages, 5604 KiB

Open AccessPerspective

Effects of Moisture on Diffusion in Unmodified Wood Cell Walls: A Phenomenological Polymer Science Approach

by Joseph E. Jakes, Christopher G. Hunt, Samuel L. Zelinka, Peter N. Ciesielski and Nayomi Z. Plaza

Forests 2019, 10(12), 1084; https://doi.org/10.3390/f10121084 - 29 Nov 2019

Cited by 65 | Viewed by 8917

Abstract

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 [...] Read more.

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. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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19 pages, 2785 KiB

Open AccessPerspective

Wood Moisture-Induced Swelling at the Cellular Scale—Ab Intra

by Xavier Arzola-Villegas, Roderic Lakes, Nayomi Z. Plaza and Joseph E. Jakes

Forests 2019, 10(11), 996; https://doi.org/10.3390/f10110996 - 7 Nov 2019

Cited by 40 | Viewed by 5639

Abstract

Wood, a complex hierarchical material, continues to be widely used as a resource to meet humankind’s material needs, in addition to providing inspiration for the development of new biomimetic materials. However, for wood to meet its full potential, researchers must overcome the challenge [...] Read more.

Wood, a complex hierarchical material, continues to be widely used as a resource to meet humankind’s material needs, in addition to providing inspiration for the development of new biomimetic materials. However, for wood to meet its full potential, researchers must overcome the challenge of understanding its fundamental moisture-related properties across its many levels of hierarchy spanning from the molecular scale up to the bulk wood level. In this perspective, a review of recent research on wood moisture-induced swelling and shrinking is presented from the molecular level to the cellular scale. Numerous aspects of swelling and shrinking in wood remain poorly understood, sub-cellular phenomena in particular, because it can be difficult to study them experimentally. Here, we discuss recent research endeavors at each of the relevant length scales, including the molecular, cellulose elementary fibril, secondary cell wall layer nanostructure, cell wall, cell, and cellular levels. At each length scale, we provide a discussion on the current knowledge and suggestions for future research. The potential impacts of moisture-induced swelling pressures on experimental observations of swelling and shrinking in wood at different length scales are also recognized and discussed. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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12 pages, 1110 KiB

Open AccessPerspective

On the Experimental Assessment of the Molecular-Scale Interactions between Wood and Water

by Nayomi Z. Plaza

Forests 2019, 10(8), 616; https://doi.org/10.3390/f10080616 - 25 Jul 2019

Cited by 26 | Viewed by 3009

Abstract

Although molecular-scale wood-water interactions needed for moisture-durability can lead to the accelerated development of moisture-durable products, these interactions are often experimentally elusive. In this perspective, the topic’s state of the art understanding will be discussed, excluding computational work. Recent research efforts based on [...] Read more.

Although molecular-scale wood-water interactions needed for moisture-durability can lead to the accelerated development of moisture-durable products, these interactions are often experimentally elusive. In this perspective, the topic’s state of the art understanding will be discussed, excluding computational work. Recent research efforts based on infrared spectroscopy methods have provided new insights in terms of the accessibility of the wood polymers and moisture-induced polymer dynamics. Likewise, neutron scattering and nuclear magnetic relaxometry experiments have shown that bound water can be found within more than one local environment inside the cell wall. However, a majority of the experiments have focused on studying extracted or derived polymers instead of unmodified wood. Thus, in this paper some of the questions that still need to be addressed experimentally will also be highlighted. Full article

(This article belongs to the Special Issue Wood-Moisture Relations)

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