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Archeological wood conservation with selected organosilicon compounds studied by XFM and nanoindentation
AbstractWaterlogged wood conservation is a complex and challenging task. Detailed knowledge about the interactions between the applied chemicals and wood is necessary to ensure the effective and safe conservation of wooden artifacts. The present research aims to determine the mechanism of dimensional stabilization of archeological wood by organosilicon compounds using the combination of synchrotron-based X-ray fluorescence microscopy (XFM) and nanoindentation. Archeological oak wood was treated with methyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, or 1,3-bis-[(diethylamino)-3-(propoxy)propan-2-ol]-1,1,3,3-tetramethyldisiloxane, which in previous studies were found to be more effective than other organosilicons in stabilizing wood dimensions. The XFM and nanoindentation results showed that all three organosilicons infiltrated wood cell walls and enhanced their mechanical properties. The XFM also showed that part of the chemicals filled some void spaces like cell lumina. Based on the results obtained here and in our previous research, it is determined that the mechanism of archeological wood dimensional stabilization by organosilicon treatment is complex and likely involves both filling cell lumina and infiltration into cell walls where organosilicons interact with wood polymers.
How thermal treatment affects the chemical composition and the physical, mechanical and swelling properties of Scots pine juvenile and mature wood
AbstractHigh variations in juvenile wood properties in the radial direction and its worse performance than mature wood make it less suitable for some applications and often treated as waste material. This study aimed to assess how thermal modification affects the chemical composition and the physical, mechanical and swelling properties of Scots pine juvenile and mature wood. An additional goal was to evaluate if the modification can equalise the differences in selected properties of juvenile wood to those of mature wood so that from waste material, juvenile wood can become a fully-fledged raw material for various industrial applications. Thermal treatment at 220 °C influenced wood chemical composition, degrading mainly hemicelluloses but also affecting cellulose and lignin, which resulted in a reduction of hydroxyls and carbonyl/carboxyl groups. These changes were more pronounced for mature than juvenile wood. It reduced mass loss and swelling rate, and increased swelling pressure in the tangential and radial directions to a higher degree for juvenile than mature wood. Changes in mechanical properties in compression were statistically significant only for mature wood, while wood hardness remained unaffected. Although the applied heat treatment improved the performance of juvenile wood by reducing its swelling rate, it did not equalise the examined properties between juvenile and mature wood. Since higher juvenile wood proportion is expected in the wood supply from the future intensively managed forests, there is still a need to find suitable modification methods or better processing techniques so that instead of being thrown away as waste, it could be used broadly in various industrial applications.
Nanocellulose-Based Films for Surface Protection of Wooden Artefacts
This research investigated the selected properties of nanocellulose films intended to serve as protective patches on fissured surfaces of wooden artefacts. The effects of their plasticisation with glycerol and functionalisation with selected silanes ((3-Glycidyloxypropyl)trimethoxysilane, and Methyltrimethoxysilane) were also determined. The obtained pure cellulose nanopapers (CNPs) had a homogeneous and compact structure but were very brittle, stiff, and wavy. Functionalisation with silanes made their structure more packed and reduced their equilibrium moisture content by 87–96%, depending on the type and concentration of the silane. Silane functionalisation also slightly improved nanopapers’ resistance to moulds. Plasticisation with glycerol provided CNPs with higher flexibility and resistance to fracture and made them flatter and smoother, reducing the wettability of their surfaces but increasing their hygroscopicity (EMC values increased 1.7–3.5 times for pure CNPs and 5–33 times for functionalised CNPs) and vulnerability to mould infestation. All prepared nanopapers can be easily glued to the wood surface and colour-matched using a nitro wood stain, oil paint or waterborne acrylic paint. The research showed that cellulose nanopapers modified with silanes and plasticised with glycerol seem to be a promising solution for protecting the cracked surface of wooden artefacts against further degradation due to external conditions.
Swelling Behaviour of Bamboo (Phyllostachys pubescens)
Bamboo is a plant with various applications. As a natural, renewable material that exhibits good mechanical performance, it seems to be an interesting alternative to wood, which has become a scarce and expensive commodity. However, comprehensive knowledge of its properties is necessary to maximise its potential for various industrial purposes. The swelling behaviour of bamboo is one of the features that has not yet been sufficiently investigated. Therefore, in this research, we aimed to measure and analyse the swelling pressure and kinetics of bamboo blocks. The results show that similar to wood, the swelling kinetics of bamboo depend on its density: the denser the tissue, the higher the maximum swelling value recorded. The maximum tangential swelling measured was about 5%–6%, which is lower than the value for the most commonly used wood species. Swelling pressure ranged from 1.16 MPa to 1.39 MPa, depending on the bamboo density: the denser the sample, the shorter the time required to reach maximum swelling pressure. Like in wood, the smallest linear increase in size due to swelling was observed in the longitudinal direction (0.71%). However, opposite to wood, more pronounced swelling was recorded in the radial direction (over 7%) than in the tangential direction (nearly 6%). The results show that bamboo’s swelling behaviour makes it a good material for use in variable humidity conditions, being more favourable than the unmodified wood of many species.
Bioethanol Production from Lignocellulosic Biomass—Challenges and Solutions
Regarding the limited resources for fossil fuels and increasing global energy demands, greenhouse gas emissions, and climate change, there is a need to find alternative energy sources that are sustainable, environmentally friendly, renewable, and economically viable. In the last several decades, interest in second-generation bioethanol production from non-food lignocellulosic biomass in the form of organic residues rapidly increased because of its abundance, renewability, and low cost. Bioethanol production fits into the strategy of a circular economy and zero waste plans, and using ethanol as an alternative fuel gives the world economy a chance to become independent of the petrochemical industry, providing energy security and environmental safety. However, the conversion of biomass into ethanol is a challenging and multi-stage process because of the variation in the biochemical composition of biomass and the recalcitrance of lignin, the aromatic component of lignocellulose. Therefore, the commercial production of cellulosic ethanol has not yet become well-received commercially, being hampered by high research and production costs, and substantial effort is needed to make it more widespread and profitable. This review summarises the state of the art in bioethanol production from lignocellulosic biomass, highlights the most challenging steps of the process, including pretreatment stages required to fragment biomass components and further enzymatic hydrolysis and fermentation, presents the most recent technological advances to overcome the challenges and high costs, and discusses future perspectives of second-generation biorefineries.
Conservation of model degraded pine wood with selected organosilicons studied by XFM and nanoindentation
Organosilicon compound reactivity with biologically and chemically degraded Scots pine as determined by 1H–13C HSQC NMR
The effect of organosilicon compounds on the nanostructure of waterlogged archeological oak studied by neutron and X-ray scattering
Effects of Biological and Chemical Degradation on the Properties of Scots Pine Wood—Part I: Chemical Composition and Microstructure of the Cell Wall
Research on new conservation treatment for archaeological wood requires large amounts of wooden material. For this purpose, artificial wood degradation (biological—using brown-rot fungus Coniophora puteana, and chemical—using NaOH solution) under laboratory conditions was conducted to obtain an abundance of similar samples that mimic naturally degraded wood and can serve for comparative studies. However, knowledge about its properties is necessary to use this material for further study. In this study, the chemical composition and microstructure of degraded cell walls were investigated using FT-IR, XRD, helium pycnometry and nitrogen absorption methods. The results show that biological degradation caused the loss of hemicelluloses and celluloses, including the reduction in cellulose crystallinity, and led to lignin modification, while chemical degradation mainly depleted the amount of hemicelluloses and lignin, but also affected crystalline cellulose. These changes affected the cell wall microstructure, increasing both surface area and total pore volume. However, the chemical degradation produced a greater number of mesopores of smaller size compared to fungal decomposition. Both degradation processes weakened the cell wall’s mechanical strength, resulting in high shrinkage of degraded wood during air-drying. The results of the study suggest that degraded wood obtained under laboratory conditions can be a useful material for studies on new consolidants for archaeological wood.
Reactivity of Waterlogged Archeological Elm Wood with Organosilicon Compounds Applied as Wood Consolidants: 2D 1H–13C Solution-State NMR Studies
Some organosilicon compounds, including alkoxysilanes and siloxanes, proved effective in stabilizing the dimensions of waterlogged archaeological wood during drying, which is essential in the conservation process of ancient artifacts. However, it was difficult to determine a strong correlation between the wood stabilizing effect and the properties of organosilicon compounds, such as molecular weight and size, weight percent gain, and the presence of other potentially reactive groups. Therefore, to better understand the mechanism behind the stabilization effectiveness, the reactivity of organosilicons with wood polymers was studied using a 2D 1H–13C solution-state NMR technique. The results showed an extensive modification of lignin through its demethoxylation and decarbonylation and also the absence of the native cellulose anomeric peak in siloxane-treated wood. The most substantial reactivity between wood polymers and organosilicon was observed with the (3-mercaptopropyl)trimethoxysilane treatment, showing complete removal of lignin side chains, the lowest syringyl/guaiacyl ratio, depolymerization of cellulose and xylan, and reactivity with the C6 primary hydroxyls in cellulose. This may explain the outstanding stabilizing effectiveness of this silane and supports the conclusion that extensive chemical interactions are essential in this process. It also indicates the vital role of a mercapto group in wood stabilization by organosilicons. This 2D NMR technique sheds new light on the chemical mechanisms involved in organosilicon consolidation of wood and reveals what chemical characteristics are essential in developing future conservation treatments.
Challenges and Prospects of Applying Nanocellulose for the Conservation of Wooden Cultural Heritage—A Review
Nanocellulose is a nanostructured form of cellulose, which retains valuable properties of cellulose such as renewability, biodegradability, biocompatibility, nontoxicity, and sustainability and, due to its nano-sizes, acquires several useful features, such as low density, high aspect ratio and stiffness, a high specific surface area, easy processing and functionalisation, and good thermal stability. All these make it a highly versatile green nanomaterial for multiple applications, including the conservation of cultural heritage. This review provides the basic characteristics of all nanocellulose forms and their properties and presents the results of recent research on nanocellulose formulations applied for conserving historical artefacts made of wood and paper, discussing their effectiveness, advantages, and disadvantages. Pure nanocellulose proves particularly useful for conserving historical paper since it can form a durable, stable coating that consolidates the surface of a degraded object. However, it is not as effective for wood consolidation treatment due to its poor penetration into the wood structure. The research shows that this disadvantage can be overcome by various chemical modifications of the nanocellulose surface; owing to its specific chemistry, nanocellulose can be easily functionalised and, thus, enriched with the properties required for an effective wood consolidant. Moreover, combining nanocellulose with other agents can also improve its properties, adding new functionalities to the developed supramolecular systems that would address multiple needs of degraded artefacts. Since the broad use of nanocellulose in conservation practice depends on its properties, price, and availability, the development of new, effective, green, and industrial-scale production methods ensuring the manufacture of nanocellulose particles with standardised properties is necessary. Nanocellulose is an interesting and very promising solution for the conservation of cultural heritage artefacts made of paper and wood; however, further thorough interdisciplinary research is still necessary to devise new green methods of its production as well as develop new effective and sustainable nanocellulose-based conservation agents, which would replace synthetic, non-sustainable consolidants and enable proper conservation of historical objects of our cultural heritage.
Thermo-mechanical properties of silane-modified composite materials based on klucel and glass microballoons
Effects of Biological and Chemical Degradation on the Properties of Scots Pine—Part II: Wood-Moisture Relations and Viscoelastic Behaviour
The present research aimed to assess the moisture properties and viscoelastic behaviour of artificially degraded pine wood, intended to serve as a model material for ongoing studies on new conservation treatments for waterlogged archaeological wood. Sorption isotherms and hydroxyl accessibility were measured using a Dynamic Vapour Sorption (DVS) system, while the investigation of the selected wood rheological properties was performed using Dynamic Mechanical Analysis (DMA). Fungal decomposition of pine by Coniophora puteana decreased the maximum equilibrium moisture content (EMC) from 20.3% to 17.7% in the first and from 19.9% to 17.1% in the second DVS run compared to undegraded pine, while chemical degradation using 50% NaOH solution increased the wood EMC to 24.6% in the first and 24.2% in the second run. The number of free hydroxyls measured for the biologically degraded sample was similar to sound wood, while chemical degradation reduced their number from 11.3 mmol g−1 to 7.9 mmol g−1. The alterations in the wood chemical composition due to different degradation processes translated into changes in viscoelastic behaviour. For biologically degraded wood, a reduction in the loss modulus and storage modulus at the temperature of 25 °C was observed compared to undegraded pine. Surprisingly, for chemically degraded pine, the values were more similar to sound wood due to the considerable densification of the material resulting from shrinkage during drying. The loss factor values for both degraded wood types were higher than for undegraded ones, indicating an increase in damping properties compared to sound pine. Distinct changes were visible in the storage modulus and loss factor graphs for DMA of chemically and biologically degraded pine. The degradation processes used in the study produced wood types with different moisture and viscoelastic properties. However, both seem useful as model materials in the research on the new conservation agents for waterlogged archaeological wood.
Characterizing the chemistry of artificially degraded Scots pine wood serving as a model of naturally degraded waterlogged wood using1H–13C HSQC NMR
AbstractChemically and biologically degraded Scots pine wood was prepared as a model material for the research on new conservation agents for waterlogged archeological wood. In this study, the model wood was characterized using a 2D1H–13C solution-state NMR technique without derivatization, isolation, or extraction to assess the effect of applied degradation processes on its chemical composition and structure. The results clearly show how the two artificially degraded model wood types are chemically different. Biological decay by the brown-rot fungus Coniophora puteana caused degradation of wood polysaccharides, with heavy depletion in arabinan, mannan, and galactan, along with an increase in the cellulose's reducing ends (i.e., lowering the degree of polymerization) and partial deacetylation of mannan. The fungus cleaved roughly one-fifth of the β-aryl ethers in lignin, leading to a broadening effect on the lignin aromatic unit contours; other lignin sidechains were left untouched. Chemical degradation by NaOH hydrolysis resulted in a depletion in mannan, galactan, and glucan, as well as efficient deacetylation of mannan. It also decreased lignin content, causing changes in its structure; minor β-aryl ether cleavage along with substantial phenylcoumaran cleavage were evident. Detailed knowledge about the chemical composition and structure of artificially degraded model pine wood obtained in this research is necessary to understand the reactivity of these wood types with chemicals used for their conservation. This research will help explain the differences in the stabilization effectiveness observed between these wood types treated during conservation and understand the stabilization mechanisms, thus contributing to developing new, more effective conservation agents for wooden artifacts of Cultural Heritage.
The effect of silane modification on selected properties of gap fillers for wooden artefacts exposed outdoors
Sodium Alginate as a Green Consolidant for Waterlogged Wood—A Preliminary Study
Traditional consolidants commonly used for waterlogged wood conservation often present long-term drawbacks, prompting research into new and reliable alternatives. Reducing reliance on fossil-based chemicals that are harmful to people, the environment, and the climate is a growing trend, and sustainable materials are now being explored as alternative consolidants for conserving waterlogged archaeological wood. Among these bio-based products, sodium alginate, a natural polysaccharide, has shown promising potential. This study aimed to evaluate its effectiveness in stabilising dimensions of severely degraded archaeological elm wood during drying. Various treatments were tested, and dimensional stabilisation (ASE), weight percent gain (WPG), and volumetric shrinkage (Vs) were assessed. Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) were used to evaluate alginate penetration and interactions with residual wood components. Results indicated that the effectiveness of sodium alginate depends on the treatment method, with the soaking approach and slow drying providing the highest WPG and the best stabilisation without altering the natural wood colour. Although the best achieved anti-shrink efficiency of 40% is insufficient from the conservation perspective, sodium alginate has proven to be a promising consolidant for the conservation of waterlogged wood. Further studies will focus on enhancing its penetration and interactions with residual wood components.
Biodegradable Polymers in Veterinary Medicine - A Review
During the past two decades, tremendous progress has been made in the development of biodegradable polymeric materials for various industrial applications, including human and veterinary medicine. They are promising alternatives to commonly used non-degradable polymers to combat the global plastic waste crisis. Among biodegradable polymers used, or potentially applicable to, veterinary medicine are natural polysaccharides, such as chitin, chitosan, and cellulose as well as various polyesters, including poly(ε-caprolactone), polylactic acid, poly(lactic-co-glycolic acid), and polyhydroxyalkanoates produced by bacteria. They can be used as implants, drug carriers, or biomaterials in tissue engineering and wound management. Their use in veterinary practice depends on their biocompatibility, inertness to living tissue, mechanical resistance, and sorption characteristics. They must be designed specifically to fit their purpose, whether it be: (1) facilitating new tissue growth and allowing for controlled interactions with living cells or cell-growth factors, (2) having mechanical properties that address functionality when applied as implants, or (3) having controlled degradability to deliver drugs to their targeted location when applied as drug-delivery vehicles. This paper aims to present recent developments in the research on biodegradable polymers in veterinary medicine and highlight the challenges and future perspectives in this area.
