Polyfurfuryl alcohol (PFA) is one of the most intriguing polymers because, despite its easy polymerization in acid environment, its molecular structure is definitely not obvious. Many studies have been performed in recent decades, and every time, surprising aspects came out. With the present study, we aim to take advantage of all of the findings of previous investigations and exploit them for the interpretation of the completely cured PFA spectra registered with three of the most powerful techniques for the characterization of solid, insoluble polymers: Solid-State 13C-NMR, Attenuated Total Reflectance (ATR), Fourier Transform Infrared (FTIR) spectroscopy, and UV-resonant Raman spectroscopy at different excitation wavelengths, using both an UV laser source and UV synchrotron radiation. In addition, the foreseen structures were modeled and the corresponding 13C-NMR and FTIR spectra were simulated with first-principles and semi-empiric methods to evaluate their matching with experimental ones. Thanks to this multi-technique approach, based on complementary analytical tools and computational support, it was possible to conclude that, in addition to the major linear unconjugated polymerization, the PFA structure consists of Diels-Alder rearrangements occurring after the opening of some furanic units, while the terminal moieties of the chain involves γ-lactone arrangements. The occurrence of head-head methylene ether bridges and free hydroxyl groups (from unreacted furfuryl alcohol, FA, or terminal chains) could be excluded, while the conjugated systems could be considered rather limited.
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).
Tannin foams are green lightweight materials that have attracted industrial interest for the manufacturing of sandwich panels for insulation purposes. However, the dimensions of the cells and the presence of sulfur in the formulation developed until now have discouraged their upscaling. In this work, we present the synthesis and the characterization of the more promising small cell and sulfur-free materials. It was observed that, with respect to standard ones, foams catalyzed with nitric acid present similar physical properties and more phenolic character, which favors the absorption of ionic pollutants. Conversely, the foams blown with aliphatic solvents and surfactants present smaller pores, and higher mechanical and insulating properties, without affecting the chemical properties or the heating value. The combined foam produced with nitric acid as a catalyst and petroleum ether as a blowing agent result in sulfur-free and small cell material with overall improved features. These foams have been produced at 30 × 30 × 3 cm3, with high homogeneity and, to date, they represent the most suitable formulation for industrial upscaling.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.