Tannin-Based Hybrid Materials and Their Applications: A Review.

Tannins are eco-friendly, bio-sourced, natural, and highly reactive polyphenols. In the past decades, the understanding of their versatile properties has grown substantially alongside a continuously broadening of the tannins' application scope. In particular, recently, tannins have been increasingly investigated for their interaction with other species in order to obtain tannin-based hybrid systems that feature advanced and/or novel properties. Furthermore, in virtue of the tannins' chemistry and their high reactivity, they either physicochemically or physically interact with a wide variety of different compounds, including metals and ceramics, as well as a number of organic species. Such hybrid or hybrid-like systems allow the preparation of various advanced nanomaterials, featuring improved performances compared to the current ones. Consequently, these diverse-shaped materials have potential use in wastewater treatment or catalysis, as well as in some novel fields such as UV-shielding, functional food packaging, and biomedicine. Since these kinds of tannin-based hybrids represent an emerging field, thus far no comprehensive overview concerning their potential as functional chemical building blocks is available. Hence, this review aims to provide a structured summary of the current state of research regarding tannin-based hybrids, detailed findings on the chemical mechanisms as well as their fields of application.

Robustness of texture-based roundwood tracking.

The proof of origin of wood logs is becoming more and more important. In the context of Industry 4.0 and to combat illegal logging, there is an increased interest to track each individual log. There were already previous publications on wood log tracing using image data from logs, but these publications used experimental setups that cannot simulate a practical application where logs are tracked between different stages of the wood processing chain, like e.g. from the forest to the sawmill. In this work, we employ image data from the same 100 logs that were acquired at different stages of the wood processing chain (two datasets at the forest, one at a laboratory and two at the sawmill including one acquired with a CT scanner). Cross-dataset wood tracking experiments are applied using (a) the two forest datasets, (b) one forest and the RGB sawmill dataset and (c) different RGB datasets and the CT sawmill dataset. In our experiments we employ two CNN based method, 2 shape descriptors and two methods from the biometric areas of iris and fingerprint recognition. We will show that wood log tracing between different stages of the wood processing chain is feasible, even if the images at different stages are obtained at different image domains (RGB-CT). But it only works if the log cross sections from different stages of the wood processing chain either offer a good visibility of the annual ring pattern or share the same woodcut pattern.

Microwave-Assisted Lignin Extraction-Utilizing Deep Eutectic Solvents to Their Full Potential.

The current research intended to investigate the suitability of different choline-chloride-based deep eutectic solvents for their role in microwave lignin extraction. Lignin, a widely spread biopolymer in plants and woody structures, is a valuable replacement for fossil-fuel-based materials. While some promising applications have been trialled already, the extraction of this material from its matrix still causes problems. Here, we highlight an efficient and fast method to extract lignin from untreated larch bark with deep eutectic solvents in a standard domestic microwave. We developed a straightforward, green methodology, which can be used on various reaction scales, with materials available to many researchers. Lignin was extracted within only 30 min of microwave irradiation in yields of up to 96%. Compared to traditional deep eutectic extraction by conventional heating, the reaction time was cut by 87% and the energy costs were reduced by 93.5%. The hydrogen bond donors were exchanged and different types, namely acid-based, hydroxyl-based and amide-based donor systems, were evaluated for their suitability concerning microwave lignin extraction. This study presents a novel approach towards energy-efficient and green lignin valorisation, without the inherent need for costly equipment.

Physical-Mechanical Properties of Peat Moss (Sphagnum) Insulation Panels with Bio-Based Adhesives.

Rising energy and raw material prices, dwindling resources, increased recycling, and the need for sustainable management have led to growth in the smart materials sector. In recent years, the importance and diversity of bio-based adhesives for industrial applications has grown steadily. This article focuses on the production and characterization of insulation panels consisting of peat moss and two bio-based adhesives. The panels were pressed with tannin and animal-based resins and compared to panels bonded with urea formaldehyde. The physical-mechanical properties, namely, thermal conductivity (TC), water vapor diffusion resistance, modulus of rupture (MOR), modulus of elasticity (MOE), internal bond (IB), compression resistance (CR), water absorption (WA) and thickness swelling (TS) were measured and analyzed. The results show that the insulation effectiveness and mechanical stability of moss panels bound with tannin and animal glue are comparable to standard adhesives used in the composite industry.

Mechanical Properties of Cellulose and Flax Fiber Unidirectional Reinforced Plywood.

This research presents the influence of two different cellulose (hydrophobic pretreated/non-pretreated) and one flax-fiber unidirectional nonwoven low areal weight fiber reinforcements on the mechanical properties of urea-formaldehyde bonded five layered beech (Fagus sylvatica L.) plywood as an alternative to commonly used synthetic fiber reinforcements. The results display divergent trends regarding the improvement of the mechanical properties-modulus of elasticity, modulus of rupture, tensile strength, shear strength, and screw withdrawal resistance. The non-treated cellulose and flax reinforcing nonwoven fabrics revealed similar mechanical behaviors. The hydrophobic pretreatment of cellulose nonwovens improved the performance of plywood regarding tensile strength (10-11%), shear strength (7-16%), screw withdrawal resistance (11-15%), and modulus of rupture (0-2%), but lowered modulus of elasticity (2-3%) compared to the reference.

Fire Retardancy of Cementitious Panels with Larch and Spruce Bark as Bio-Admixtures.

The aim of this study is to investigate the production of fire-resistant panels made out of bark from spruce (Picea abies), larch (Larix decidua Mill.) and cement. This research included test panels produced from bark, cement, water and cement-bonded recycling material aiming for the target density of 750 kg/m3. The physical (density, dimension stability, thickness swelling) and mechanical properties such as tensile strength and compressive strength together with fire resistance were tested. Considering the results, appealing values have been achieved: max. compressive strength: 3.42 N/mm2; max. thickness swelling: 5.48%; and density: 515 to 791 kg/m3. In principle, the properties of the produced panels depend not only on the density, but also on the hydration and, above all, on the compaction and the composition of the boards. The fire tests demonstrated that the produced panels have an enormous potential in terms of fire resistance and could be utilized for fire-retardant applications.

Organosolv Lignin from European Tree Bark: Influence of Bark Pretreatment.

As lignin is becoming more and more attractive to industry and the circular economy continues to grow, the utilization of a byproduct that, to date, has been underrated by the wood industry is investigated as an abundantly available source of lignin. Bark from spruce, larch and beech tress is extracted using the organosolv process with and without prior hot water extraction. The influence of the treatment on chemical properties of the lignin was determined by spectrophotometric, chromatographic, and vibrational spectroscopy. It was found that hot water extraction prior to organosolv extraction influences the chemical composition, antioxidative properties and molecular weight distribution of the obtained extracts. While hot water extracts are rich in flavonoids, organosolv fractions can contain high amounts of organic acids depending on whether they are from a hardwood or softwood source. This investigation lays the foundation for further research into the utilization of byproducts to generate high-value resources.

Tannin-Furanic Foams Formed by Mechanical Agitation: Influence of Surfactant and Ingredient Ratios.

With increasing demand of alternatives to oil-based lightweight materials, the development of tannin-based foams is getting more and more attention. In this paper, an alternative to traditionally used solvent-evaporation in the production of tannin-foams is presented. Mixing the tannin-furanic resin with different amounts of ionic and non-ionic surfactants at high agitational speed allows for the formation of highly porous, mechanically stable tannin-foams. Investigations on the influence of surfactant type and ingredient ratios on the foaming behavior and properties of the final foams were conducted. Materials obtained via this route do present extraordinary compression resistance (about 0.8 MPa), good thermal insulation (40 mW/m·K) and are suitable as a wastewater treatment agent at the end-of-life. It was shown that during mechanical blowing, homogeneous cross-sections and almost perfectly round pores form, leading to the high compression resistance. Investigations by means of Fourier transform infrared and 13C nuclear magnetic resonance spectroscopy show that the milder reaction environment leads to more linear poly(furfuryl alcohol)-tannin chains. This new type of tannin foam allows for use in various different fields of application ranging from durable building insulation to wastewater treatment.

Changing in Larch Sapwood Extractives Due to Distinct Ionizing Radiation Sources.

Wood extractives have an influence on different material properties. This study deals with the changes in wood extractives of larch sapwood due to two different low doses of energy irradiations. Electron beam irradiation (EBI) and γ-ray irradiation treatments were done by using two industrial processes. After the different modifications the extractions were performed with an accelerated solvent extractor (ASE) using hexane and acetone/water. The qualitative and quantitative chemical differences of irradiated larch sapwood samples were analysed using gas chromatography-mass spectrometry (GC-MS) and Fourier-transform infrared spectroscopy (FT-IR) vibrational spectroscopy methods. The yields of the quantitative extractions decreased due to the two different irradiation processes. While the compounds extracted with nonpolar solvent from wood were reduced, the number of compounds with polar functionalities increased based on the oxidation process. Quantitatively, resin acids and polyphenols were highly affected when exposed to the two irradiation sources, leading to significant changes (up, down) in their relative amount. Furthermore, two new substances were found in the extracts of larch sapwood samples after EBI or γ-ray treatments. New insight into the different effects of larch sapwood and wood extractives by EBI and γ-ray was gained in this study.

Binderless Thermal Insulation Panels Made of Spruce Bark Fibres.

Tree bark is a by-product of the timber industry available in large amounts, considering that approximately 10% of the volume of a tree stem is bark. Bark is used primarily for low-value applications such as heat generation or as mulch. To the best of our knowledge, this study is the first one that scrutinises thermal insulation panels made from spruce bark fibres with different densities and fibre lengths manufactured in a wet process. The insulation boards with densities between 160 and 300 kg/m3 were self-bonded. Internal bond, thermal conductivity, and dimensional stability (thickness swelling and water absorption), together with formaldehyde content, were analysed. The thermal properties of the boards were directly correlated with the density and reached about 0.044 W/m*K, while the internal bond was rather influenced by the fibre length and was relatively low (on average 0.07 N/mm2). The water absorption was high (from 55% to 380%), while the thickness swelling remained moderate (up to 23%). The results of this study have shown that widely available bark residues can be successfully utilised as an innovative raw material for efficient eco-friendly thermal insulation products.

Influence of Adhesive Systems on the Mechanical and Physical Properties of Flax Fiber Reinforced Beech Plywood.

In order to improve the acceptance of broader industrial application of flax fiber reinforced beech (Fagus sylvatica L.) plywood, five different industrial applicated adhesive systems were tested. Epoxy resin, urea-formaldehyde, melamine-urea formaldehyde, isocyanate MDI prepolymer, and polyurethane displayed a divergent picture in improving the mechanical properties-modulus of elasticity, modulus of rupture, tensile strength, shear strength and screw withdrawal resistance-of flax fiber-reinforced plywood. Epoxy resin is well suited for flax fiber reinforcement, whereas urea-formaldehyde, melamine urea-formaldehyde, and isocyanate prepolymer improved modulus of elasticity, modulus of rupture, shear strength, and screw withdrawal resistance, but lowered tensile strength. Polyurethane lowered the mechanical properties of flax fiber reinforced plywood. Flax fiber reinforced epoxy resin bonded plywood exceeded glass fiber reinforced plywood in terms of shear strength, modulus of elasticity, and modulus of rupture.

Method to Investigate Multi-Axis Release Action of Ski Safety Bindings: A New Approach for Testing in Research and Development.

The authors developed and elaborated on a new method to release ski bindings by utilizing an industrial robot to simulate release movement showing a spatial repeatability of ± 0.06 mm. The parametric programming of the release parameters gave free control while executing repeatable release tests. A series of different motion patterns were performed, on the one hand, to test the applicability of the setup to the simulation of motion patterns and, on the other, to check for the impact of the ski deformations like ski deflections within the range of -5 mm to -85 mm, on the safety bindings' release forces. As certain falling mechanisms are related to knee injury, which is the most common severe injury in alpine skiing, this testing method can be used to develop related displacement movements in future. This movements do not necessarily accord with the directional release mechanics of safety ski bindings. The authors specify the developed testing apparatus as device for force measurements in 3D with an accuracy of ± 0.5% in boot-sole-plane. The intention behind this development is to enable faster, more versatile and adaptive testing procedures in R&D.

Production and Physical-Mechanical Characterization of Peat Moss (Sphagnum) Insulation Panels.

Peat moss (sphagnum) is a commonly used sealant, fill, and insulation material in the past. During the efforts to rewet drained moors due to ecological considerations, the technical use of peat moss (sphagnum farming) again became the focus of attention. In the framework of this investigation, insulation panels consisting of peat moss, bound with urea formaldehyde, were produced. Panels manufactured in a wet process and mats bound with textiles were also fabricated. The specimens' thermal conductivity, water vapor diffusion resistance, modulus of rupture, modulus of elasticity, internal bond, compression resistance, water absorption, and thickness swelling were measured. Physical-mechanical properties were adequate with the resin-bound panels, but not with wet process panels. Moss mats had good characteristics for cavity insulation purposes. The thermal conductivity of the moss panels and mats was found to be lowest with a density of 50 kg/m3, accounting for 0.04 W/m·K. The results show that peat moss is a promising resource for production insulation panels, because their thermal conductivity and mechanical stability are comparable to other insulation materials.

Efficiency of High-Frequency Pressing of Spruce Laminated Timber Bonded with Casein Adhesives.

This study identifies the importance of reducing press times by employing high-frequency pressing of spruce-laminated timber bound with sustainable casein adhesives. Spruce lamellas with dimensions of 12 × 10 × 75 cm were bonded into five-layered laminated timber and then separated into single-layer solid wood panels. Three types of casein (acid casein from two sources and rennin) were used. To compare the effectiveness of the casein formulation, two control samples bonded with polyvinyl acetate (PVAc) adhesive were pressed at room temperature (20 °C) and also with high-frequency equipment. The tests included compression shear strength, modulus of rupture, modulus of elasticity and screw withdrawal resistance on the wood panel surface and in the glue line. The average values of casein-bonded samples compression strengths ranged from 1.16 N/mm2 and 2.28 N/mm2, for modulus of rupture (MOR) were measured 85 N/mm2 to 101 N/mm2 and for modulus of elasticity (MOE) 12,200 N/mm2 to 14,300 N/mm2. The screw withdrawal resistance (SWR) on the surface of the wood panels ranged from 91 N/mm to 117 N/mm and in the adhesive line from 91 N/mm to 118 N/mm. Control samples bonded with PVAc adhesive did not perform better for compression shear strength, MOR and MOE, but for SWR in the adhesive line with 114 N/mm. Casein-bonded spruce timber pressed with HF equipment represents a sustainable new product with reduced press times, hazardous emissions and improved workability.

Selected Properties of Cement Bound Spruce and Larch Bark Bio-Aggregates.

The aim of this study is to investigate the suitability of spruce and larch bark for the production of cement-bonded composites. At the beginning of this research, the curing behaviour of the admixtures was quantified with temperature profiles when testing spruce, larch, pine and poplar bark, to determine the compatibility between the components of the bio-aggregates, to analyse the cement curing and to establish which bark species should be successfully included in cement bonded composites. Considering the results, it was observed that the average densities of 600-700 kg/m3 of bio-aggregates are 40-55% lower than that of established products on the market, although spruce and larch bark are in a similar range. The situation is different for the compressive strength, as larch bark showed up to 30% higher values than spruce bark. This study revealed also different hardening characteristics of the two cement types used as binders for spruce and larch bark. The results of this study demonstrated that tree bark of Picea abies and Larix decidua Mill. can be successfully utilized for the production of a cement-bonded composite material.

Oversized Planer Shavings for the Core Layer of Lightweight Particleboard.

Planer shavings (PS) are side-products generated during the processing of solid wood, typically used for heating, packaging, or insulation purposes. PS has been used for decades in particleboard manufacture, particularly in the core layer. The aim of this research is to investigate the use of PS with a length over 4 mm in low-density one-layer particleboard manufacturing with a thickness of 10 mm, as an option to reduce the raw material demand for wood-based panels. Correlations towards the mechanical properties of the particleboards, fabricated at a density of 475 kg/m3, could be drawn by analyzing the effects of different urea-formaldehyde adhesive contents (6%, 9%, and 12%). Two methods of adhesive application (pouring and spraying) and two types of blending of PS with adhesive (plowshare mixer and drum mixer) were investigated, with the aim that PS will have controlled resin application. The difference between the adhesive application methods was examined by analyzing the mechanical properties as an internal bond, modulus of rupture, and modulus of elasticity as well as indirectly by visualizing the adhesive distribution by adding a green pigment to the adhesive before application. PS demonstrated reduced bending properties in comparison with the EN 312 standard requirements of particleboards for internal use in dry conditions (type P2), due to the low density. The internal bond strength in the case of the particleboard without pigment application (up to 0.5 N/mm2) was higher compared to the P2 requirements (0.4 N/mm2), and significantly lower (0.15 N/mm2) in combination with the pigment (2.5% based on the board weight, compared to 0.1%, specific for such industry applications), but still superior to the values of the reference panel manufactured with wood particles.

Potential of Brewer's Spent Grain as a Potential Replacement of Wood in pMDI, UF or MUF Bonded Particleboard.

Brewer's spent grain (BSG) is the richest by-product (85%) of the beer-brewing industry, that can be upcycled in a plentiful of applications, from animal feed, bioethanol production or for removal of heavy metals from wastewater. The aim of this research is to investigate the mechanical, physical and structural properties of particleboard manufactured with a mixture of wood particles and BSG gradually added/replacement in 10%, 30% and 50%, glued with polymeric diisocyanate (pMDI), urea-formaldehyde (UF) and melamine urea-formaldehyde (MUF) adhesives. The density, internal bond, modulus of rupture, modulus of elasticity, screw withdrawal resistance, thickness swelling and water absorption were tested. Furthermore, scanning electron microscopy anaylsis was carried out to analyze the structure of the panels after the internal bond test. Overall, it was shown that the adding of BSG decreases the mechanical performance of particleboard, due to reduction of the bonding between wood and BSG particles. This decrease has been associated with the structural differences proven by SEM inspection. Interaction of particles with the adhesive is different for boards containing BSG compared to those made from wood. Nevertheless, decrease in the mechanical properties was not critical for particleboards produced with 10% BSG which could be potentially classified as a P2 type, this means application in non-load-bearing panel for interior use in dry conditions, with high dimensional stability and stiffness.

Water-Resistant Casein-Based Adhesives for Veneer Bonding in Biodegradable Ski Cores.

The aim of this study is to investigate the performance of casein-based adhesives for the bonding of ash (Fraxinus spp.) veneers for the manufacture of biodegradable skis. Different formulations containing casein powder, water, lime, sodium silicate, and various glue amounts were tested for shear strength after water storage, modulus of rupture and modulus of elasticity, water absorption, and thickness swelling. Two other classic wood adhesives, namely epoxy and polyvinyl acetate (PVAc) type D4 were used as control. The highest efficiency of both mechanical and physical properties was recorded for the samples glued with caseins and an increased amount of lime. There was also an affinity between casein adhesive distribution and physical and mechanical plywood performance. Moreover, the developed casein-based glues were also used to bond the plywood for ski cores and tested in real-life winter conditions.

Larch Bark as a Formaldehyde Scavenger in Thermal Insulation Panels.

The aim of this study is to investigate the formaldehyde content and emissions of bark-based insulation panels bonded with three types of adhesives: urea formaldehyde, melamine urea-formaldehyde, and tannin-based adhesives. These panels were produced at two levels of density-300 and 500 kg/m3-and a thickness of 20 mm, and the influence of the adhesive amount and type on the formaldehyde emissions and content was measured. Other mechanical and physical properties such as modulus of rupture, modulus of elasticity, internal bond, and dimensional stability were also scrutinized. With one exception, all the panels belonged to the super E0 classification for free formaldehyde content (perforator value ≤1.5 mg/100 g oven dry mass of panels). The measurements using the desiccator method for formaldehyde emissions assigned all the testing specimens in the F **** category for low-emission panels according to the Japanese International Standards.

Mitigation of Ammonia Emissions from Cattle Manure Slurry by Tannins and Tannin-Based Polymers.

With the extensive use of nitrogen-based fertilizer in agriculture, ammonia emissions, especially from cattle manure, are a serious environmental threat for soil and air. The European community committed to reduce the ammonia emissions by 30% by the year 2030 compared to 2005. After a moderate initial reduction, the last report showed no further improvements in the last four years, keeping the 30% reduction a very challenging target for the next decade. In this study, the mitigation effect of different types of tannin and tannin-based adsorbent on the ammonia emission from manure was investigated. Firstly, we conducted a template study monitoring the ammonia emissions registered by addition of the tannin-based powders to a 0.1% ammonia solution and then we repeated the experiments with ready-to-spread farm-made manure slurry. The results showed that all tannin-based powders induced sensible reduction of pH and ammonia emitted. Reductions higher than 75% and 95% were registered for ammonia solution and cattle slurry, respectively, when using flavonoid-based powders. These findings are very promising considering that tannins and their derivatives will be extensively available due to the increasing interest on their exploitation for the synthesis of new-generation "green" materials.