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.

Walnut and hazelnut shells are agricultural by-products, available in high quantities during the harvest season. The potential of using these two agricultural residues as raw materials in particleboard production has been evaluated in this study. Different panels with either walnut or hazelnut shells in combination with melamine-urea formaldehyde or polyurethane at the same level of 1000 kg/m³ density were produced in a laboratory hot press and mechanical properties (modulus of elasticity, bending strength, and Brinell hardness) and physical properties (thickness swelling and water absorption) were determined, together with formaldehyde content. Although Brinell hardness was 35% to 65% higher for the nutshell-based panels, bending strength and modulus of elasticity were 40% to 50% lower for the melamine-urea formaldehyde bonded nutshells compared to spruce particleboards, but was 65% higher in the case of using polyurethane. Water absorption and thickness swelling could be reduced significantly for the nutshell-based boards compared to the spruce boards (the values recorded ranged between 58% to 87% lower as for the particleboards). Using polyurethane as an adhesive has benefits for water uptake and thickness swelling and also for bending strength and modulus of elasticity. The free formaldehyde content of the lignocellulosic-based panels was included in the E0 category (≤2.5 mg/100 g) for both walnut and hazelnut shell raw materials and the use of polyurethane improved these values to super E0 category (≤1.5 mg/100 g).

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.

Ecofriendly wood-based materials are required by consumers at present. Decorative panels are part of a large group of wood-composite materials, and their environmental properties must not be neglected. More environmentally friendly decorative panels can be achieved by various methods. This paper describes a method of production from larch bark. Tree bark, as a byproduct of the wood industry, is one of the research topics that have gained interest in the last decade, especially for its applications in biobased lignocomposites, with regard to the shrinkage of wood resources. In the present work, the formaldehyde content of decorative boards based on larch bark (0.6 g/cm³) was analyzed when bonded with five different types of adhesive systems: urea-formaldehyde, polyvinyl acetate, the mixture of 70% urea-formaldehyde + 30% polyvinyl acetate, polyurethane, and tannin-based adhesive. A self-agglomerated board was also analyzed. The formaldehyde content of the larch-bark samples was determined with the perforator method (EN 120:2011), and findings showed that all tested samples reached the E1 classification (≤8 mg/100 oven dry). Moreover, 75% of the values of the corrected formaldehyde content were included in the super-E0 class (≤1.5 mg/100 oven dry). In the case of boards bonded with tannin-based adhesive, this natural polymer acted as a formaldehyde scavenger.

Furfuryl alcohol is a very interesting green molecule used in the production of biopolymers. In the present paper, the copolymerization in acid environment with natural, easily-available, phenolic derivatives is investigated. The processes of polymerization of the furfuryl alcohol with: (i) spent-liquor from the pulping industry and (ii) commercial tannin from acacia mimosa were investigated though viscometry and IR-spectroscopy. The curing kinetics of the formulations highlighted the importance of the amount of furfuryl alcohol and catalyst as well as the effect of temperature for both phenolic-furanic polymers. Evidence of covalent copolymerization has been observed through infrared spectrometry (FT-IR) combined with principal component analysis (PCA) and confirmed with additional solubility tests. These bio-based formulations were applied as adhesives for solid wood and particleboards with interesting results: at 180 °C, the spent-liquor furanic formulations allow wood bonding slightly with lower performance than PVA in dry conditions, while mixed formulations allow the gluing of particleboard with only satisfactory internal bonding tests.

Tannin based rigid foams (TBRFs) have been produced with formaldehyde since 1994. Only recently several methods have been developed in order to produce these foams without using formaldehyde. TBRFs with and without formaldehyde are visually indistinguishable; therefore a method for determining the differences between these foams had to be found. The attenuated total reflectance infrared spectroscopy (ATR FT-IR) investigation of the TBRFs presented in this paper allowed discrimination between the formaldehyde-containing (classic) and formaldehyde-free TBRFs. The spectra of the formaldehyde-free TBRFs, indeed, present decreased band intensity related to the C–O stretching vibration of (i) the methylol groups and (ii) the furanic rings. This evidence served to prove the chemical difference between the two TBRFs and explained the slightly higher mechanical properties measured for the classic TBRFs.