Spray Coating of Wood with Nanoparticles from Lignin and Polylactic Glycolic Acid Loaded with Thyme Essential Oils.

Ensuring the longevity of wooden constructions depends heavily on the preservation process. However, several traditional preservation methods involving fossil-based compounds have become outdated because they pose a significant risk to the environment and to human health. Therefore, the use of bio-based and bioactive solutions, such as essential oils, has emerged as a more sustainable alternative in protecting wood from biotic attacks. The entrapment of essential oils in polymeric carrier matrices provides protection against oxidation and subsequent degradation or rapid evaporation, which implies the loss of their biocidal effect. In this work, lignin as well as PLGA nanoparticles containing the essential oils from two different thyme species (Thymus capitatus and T. vulgaris) were applied on beech wood samples using spray coating. The prepared coatings were investigated using FTIR imaging, SEM, as well as LSM analysis. Release experiments were conducted to investigate the release behavior of the essential oils from their respective lignin and PLGA carrier materials. The study found that lignin nanoparticles were more effective at trapping and retaining essential oils than PLGA nanoparticles, despite having larger average particle diameters and a more uneven particle size distribution. An analysis of the lignin coatings showed that they formed a uniform layer that covered most of the surface pores. PLGA nanoparticles formed a film-like layer on the cell walls, and after leaching, larger areas of native wood were evident on the wood samples treated with PLGA NPs compared to the ones coated with lignin NPs. The loading capacity and efficiency varied with the type of essential oil, while the release behaviors were similar between the two essential oil types applied in this study.

Extraction and Characterization of Acidolysis Lignin from Turkey Oak (Quercus cerris L.) and Eucalypt (Eucalyptus camaldulensis Dehnh.) Wood from Population Stands in Italy.

Acidolysis lignins from the species Quercus cerris L. and Eucalyptus camaldulensis Dehnh. were isolated and characterized using high pressure size exclusion chromatography (HP-SEC), Fourier-transform (FTIR) infrared spectroscopy, analytical pyrolysis-gas chromatography-mass spectrometry (Py-GCMS), and two-dimensional heteronuclear single quantum coherence (2D HSQC) NMR spectroscopy. The acidolysis lignins from the two different species varied in chemical composition and structural characteristics, with Q. cerris L. lignin having a higher S/G ratio and higher molar mass averages with a bimodal molar mass distribution. The different analytical techniques FTIR spectroscopy, Py-GCMS, and 2D NMR spectroscopy provided consistent results regarding the S/G ratio of the lignins from the two wood species. Based on the determined high S/G ratio of both oak and eucalypt lignin, the two wood sources could be promoted as substrates for efficient lignin isolation in modern forest biorefineries in order to develop innovative lignin-based value-added biorefinery products.

Lignin Nanoparticles with Entrapped Thymus spp. Essential Oils for the Control of Wood-Rot Fungi.

After decades of utilization of fossil-based and environmentally hazardous compounds for wood preservation against fungal attack, there is a strong need to substitute those compounds with bio-based bioactive solutions, such as essential oils. In this work, lignin nanoparticles containing four essential oils from thyme species (Thymus capitatus, Coridothymus capitatus, T. vulgaris, and T. vulgaris Demeter) were applied as biocides in in vitro experiments to test their anti-fungal effect against two white-rot fungi (Trametes versicolor and Pleurotus ostreatus) and two brown-rot fungi (Poria monticola and Gloeophyllum trabeum). Entrapment of essential oils provided a delayed release over a time frame of 7 days from the lignin carrier matrix and resulted in lower minimum inhibitory concentrations of the essential oils against the brown-rot fungi (0.30-0.60 mg/mL), while for the white-rot fungi, identical concentrations were determined compared with free essential oils (0.05-0.30 mg/mL). Fourier Transform infrared (FTIR) spectroscopy was used to assess the fungal cell wall changes in the presence of essential oils in the growth medium. The results regarding brown-rot fungi present a promising approach for a more effective and sustainable utilization of essential oils against this class of wood-rot fungi. In the case of white-rot fungi, lignin nanoparticles, as essential oils delivery vehicles, still need optimization in their efficacy.

Cellulose Nano Crystals (CNC) as Additive for a Bio-Based Waterborne Acrylic Wood Coating: Decay, Artificial Weathering, Physical and Chemical Tests.

Wood coatings prolong the service life of wood-based products, but they are usually of synthetic origin. The aim of the present article is to reduce the fossil-based compounds in a commercial waterborne acrylic coating by CNC addition and to test its performance. The coatings were applied on European beech and Norway spruce wood in order to test durability against Gloeophyllum trabeum (brown wood rot) and Trametes versicolor (white wood rot). Artificial weathering and blue stain, contact angle, physical tests (adhesion, impact and scratch test), chemical (FTIR) and morpho-anatomical analysis (SEM) were carried out. CNC addition increased viscosity, limiting the spreading of the coating into wood pores as visible after SEM observation, which reduced coating adhesion on the substrate. CNC improved fungal resistance as seen by a reduced mass loss and FTIR spectroscopy thanks to crosslinks formation, which reduced water sorption as well. Color change was not significant, and, on the other hand, glossiness was reduced but resulted as more homogeneous than control. CNC addition gave good results also in blue stain protection. CNC improved scratch resistance, but no visible change to impact was registered. CNC has promising results in coatings depending on wood and fungal species and presence of further commercial additives (biocides).

Synthesis and Characterizations of Eco-Friendly Organosolv Lignin-Based Polyurethane Coating Films for the Coating Industry.

Three different formulations of bio-based polyurethane (PU), varying the weight ratio between Organosolv lignin and a commercial isocyanate, were synthesized. The coating formulations were characterized by SEM, pyrolysis-GC/MS, FTIR spectroscopy and FTIR mapping, which confirmed the successful formation of urethane bonds between commercial isocyanate and hydroxyl groups deriving from lignin. The coatings were applied on beech wood samples to measure color and contact angles, and eventually FTIR mapping of the coated wood samples was performed. FTIR mapping is an interesting tool to monitor the distribution of PU chemical bonds on the coating surface and to evaluate the homogeneity of the applied coating films. Increasing the lignin content of the PU coatings results in more red-yellow and darker tones, while the commercial PU coating is transparent. For a higher lignin concentration, the solid content as well as the weight gain of the applied coatings increase. A higher percentage of lignin in the prepared PU formulations leads to superficial cracks and therefore higher coating permeability compared to the commercial PU, but the prepared lignin-based PU coating still makes a raw wood surface significantly more hydrophobic. Apparently, additives such as film-formers with low surface tension to counteract cracks' formation are necessary to improve the performance of lignin-based PU coatings.

Production and Properties of Lignin Nanoparticles from Ethanol Organosolv Liquors-Influence of Origin and Pretreatment Conditions.

Despite major efforts in recent years, lignin as an abundant biopolymer is still underutilized in material applications. The production of lignin nanoparticles with improved properties through a high specific surface area enables easier applicability and higher value applications. Current precipitation processes often show poor yields, as a portion of the lignin stays in solution. In the present work, lignin was extracted from wheat straw, spruce, and beech using ethanol organosolv pretreatment at temperatures from 160-220 °C. The resulting extracts were standardized to the lowest lignin content and precipitated by solvent-shifting to produce lignin micro- and nanoparticles with mean hydrodynamic diameters from 67.8 to 1156.4 nm. Extracts, particles and supernatant were analyzed on molecular weight, revealing that large lignin molecules are precipitated while small lignin molecules stay in solution. The particles were purified by dialysis and characterized on their color and antioxidant activity, reaching ASC equivalents between 19.1 and 50.4 mg/mg. This work gives detailed insight into the precipitation process with respect to different raw materials and pretreatment severities, enabling better understanding and optimization of lignin nanoparticle precipitation.

Influence of forest stand characteristics on physical, mechanical properties and chemistry of chestnut wood.

Site conditions and forest management affect dendrometric parameters of chestnut (Castanea sativa Mill.) coppices, but there is modest knowledge on the effect of stand dendrometric characters on physical and mechanical wood characteristics. The aim of this study was to verify these relationships in chestnut coppices that were 12-14 years old. Wood density, compression and bending strength, shrinkages were measured on shoots of five different stand in a vulcanic site in Monte Amiata (Central - Italy). Investigated stands differ in number of stools/ha and dominant height, diameter/basal area of the shoots. The main difference in the physical characters among the stands is density. The initial results of the study showed that physical, mechanical wood characters are more dependent by the shoot than by the site. There is a positive relationships between the number of stools/ha and density and a negative one among shoot dominant height and basal area with wood density. Spectroscopic profile by FTIR has not showed relevant differences among the stands. Wood anatomy has showed the breakpoint at cellular level.

Impact of Bio-Based (Tannins) and Nano-Scale (CNC) Additives on Bonding Properties of Synthetic Adhesives (PVAc and MUF) Using Chestnut Wood from Young Coppice Stands.

Sustainability and ecotoxicity issues call for innovations regarding eco-friendly adhesives in the production of biocomposite wood materials, and solutions involving nano-scale and bio-based compounds represent a valid and promising target. One possible approach is to increase the performance of adhesives such as polyvinyl acetate (PVAc) or melamine-urea-formaldehyde (MUF) by means of nanoparticles in order to obtain a material with better mechanical and environmental resistance. When applying cellulose-based nanoparticles or tannin, the concept of a circular economy is successfully implemented into the forest/wood value chain, and chances are created to develop new value chains using byproducts of forestry operations. In this study, assortments coming from young sweet chestnut (Castanea sativa Mill.) coppice stands were utilized for the preparation of single lap joint assemblies using different commercial adhesives (PVAc, MUF) and cellulose nanocrystals (CNC) and tannin as additives. The results showed that addition of CNC and tannin to PVAc glue increased tensile shear strength in lap joint tests presenting a promising base for future tests regarding the addition of CNC and tannin in MUF or PVAc adhesive formulations. Unfortunately, the tested bio-based additives did not reveal the same encouraging results when tested in the wet state.

Cellulose and Lignin Nano-Scale Consolidants for Waterlogged Archaeological Wood.

Waterlogged archaeological wood comes from submerged archaeological sites (in lake, sea, river, or wetland) or from land waterlogged sites. Even if the wooden object seems to have maintained the original size and shape, the wood is more or less severely decayed because of chemical and biological factors which modify the normal ratio of cellulose and lignin in the cell wall. Drying procedures are necessary for the musealization but potentially cause severe shrinkages and collapses. The conservation practices focus not only on removing water from wood but also on substituting it with materials able to consolidate the degraded wood cell walls like polymers (e.g., PEG), sugars (e.g., lactitol), or resins (e.g., Kauramin). In the present work three different nano-scale consolidants were tested: lignin nanoparticles (LNPs) obtained form beech wood via a non-solvent method involving dialysis; bacterial nanocellulose (BC) obtained from cultures fed with agro-alimentary waste; cellulose nanocrystals (CNC) chemically extracted from native cellulose. Waterlogged archaeological wood samples of different species (oak, elm, stone pine, and silver fir) characterized by different levels of degradation were impregnated with the consolidants. The treatments efficiency was evaluated in terms of macroscopic observation of treated samples, anti-shrink efficiency (ASE) and equilibrium moisture content (EMC). The results obtained for the three consolidants showed substantial differences: LNPs and CNCs penetrated only about a millimeter inside the treated wood, while BC formed a compact layer on the surface of the cell walls throughout the thickness of the samples. In spite of successful BC penetration, physical evaluation of treatment efficiency showed that BC nanoparticles did not obtain a satisfying consolidation of the material. Based on the reported results more focused test protocols are optimized for future consolidation experiments.

Preparation of Lignin Nanoparticles with Entrapped Essential Oil as a Bio-Based Biocide Delivery System.

Lignin isolated from beech sawdust was used for the preparation of lignin nanoparticles (LNPs) with entrapped essential oil (EO) from cinnamon bark (Cinnamomum zeylanicum Blume), common thyme (Thymus vulgaris L.), and wild thyme (Thymus serpyllum L.) using a fast antisolvent method. Analysis of EO-loaded LNPs by pyrolysis-gas chromatography-mass spectrometry and Fourier transform infrared spectroscopy confirmed molecular interaction between EOs and LNPs. Quantification of EO incorporation into the LNPs and their in vitro release profiles were assessed by reversed phase high-performance liquid chromatography. Utilized EOs were, to different extents, successfully entrapped inside LNPs, which were attributed to extensive π-stacking between aromatic compounds in EOs like cinnamaldehyde, thymol, and carvacrol on one side and aromatic lignin units on the other side. In vitro release of common thyme and wild thyme EOs from EO-loaded LNPs was strongly delayed compared to the use of pure oil, giving a promising outlook for the development of new bio-based biocide delivery systems for wood preservation.

Preparation of Lignin Nanoparticles from Wood Waste for Wood Surface Treatment.

Lignin was isolated from wood wastes comprising Iroko sawdust (IR) and mixed sawdust from Iroko and Norway spruce (IRNS), furnished by a local wood houses producer. The respective acidolysis lignin fractions were structurally characterized using pyrolysis (Py)-GCMS, two-dimensional heteronuclear single quantum correlation nuclear magnetic resonance (2D HSQC NMR), Fourier-transform infrared FTIR and ultraviolet-visible (UV-VIS) spectroscopies, size exclusion chromatography, and standard wet-chemistry methods for Klason lignin and polysaccharides determination. The isolated lignin fractions were subsequently used for the preparation of lignin nanoparticles (LNPs) using a non-solvent method. LNPs were then used for wood surface treatment using a dip-coating technique. The coated wood samples were analyzed by colorimetry and scanning electron microscopy (SEM) before and after artificial weathering experiments in a UV chamber to investigate the UV protection potential of the LNPs coatings. Wood samples dip-coated with LNPs showed promising surface modifications resembling a sort of film of fused LNPs. Coatings made from IR-LNPs and IRNS-LNPs performed significantly better in artificial weathering experiments than uncoated reference samples.