Effect of Fenton reaction parameters on the structure and properties of oxidized wheat starch.

Wheat starch was oxidized through a Fenton reaction by hydrogen peroxide and Iron II sulfate as a catalyst at various concentrations and reaction duration. The formation of carbonyl and carboxyl groups confirmed the starch oxidation as determined with Fourier-transform infrared (FTIR) spectroscopy. The degree of oxidation was estimated by carbonyl and carboxyl titration. The various oxidized wheat starches presented considerable variations in their oxidation level as a function of the catalyst concentration and oxidative process duration. The effect of the Fenton reaction parameters on the starch macromolecular chains and microstructure was evaluated by X-ray diffraction and amylose content estimation. Significant depolymerization of the starch macromolecules was observed, mainly in the starch amorphous phase, followed by a degradation of the crystalline phase at a higher oxidation level. SEM observations revealed changes in starch structure, which ranged from minor degradation of the starch granules to a more crosslinked morphology.

Fungal behavior and recent developments in biopulping technology.

Biological pretreatment of wood chips by fungi is a well-known approach prior to mechanical- or chemical pulp production. For this biological approach, a limited number of white-rot fungi with an ability to colonize and selectively degrade lignin are used to pretreat wood chips allowing the remaining cellulose to be processed for further applications. Biopulping is an environmentally friendly technology that can reduce the energy consumption of traditional pulping processes. Fungal pretreatment also reduces the pitch content in the wood chips and improves the pulp quality in terms of brightness, strength, and bleachability. The bleached biopulps are easier to refine compared to pulps produced by conventional methodology. In the last decades, biopulping has been scaled up with pilot trials towards industrial level, with optimization of several intermediate steps and improvement of economic feasibility. Nevertheless, fundamental knowledge on the biochemical mechanisms involved in biopulping is still lacking. Overall, biopulping technology has advanced rapidly during recent decades and pilot mill trials have been implemented. The use of fungi as pretreatment for pulp production is in line with modern circular economy strategies and can be implemented in existing production plants. In this review, we discuss some recent advances in biopulping technology, which can improve mechanical-, chemical-, and organosolv pulping processes along with their mechanisms.

Properties and Emissions of Three-Layer Particleboards Manufactured with Mixtures of Wood Chips and Partially Liquefied Bark.

Partial liquefaction of residual biomass shows good potential for developing new materials suitable for making bio-based composites. Three-layer particleboards were produced by replacing virgin wood particles with partially liquefied bark (PLB) in the core or surface layers. PLB was prepared by the acid-catalyzed liquefaction of industrial bark residues in polyhydric alcohol. The chemical and microscopic structure of bark and residues after liquefaction were evaluated by means of Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM), while the particleboards were tested for their mechanical and water-related properties, as well as their emission profiles. Through a partial liquefaction process, some FTIR absorption peaks of the bark residues were lower than those of raw bark, indicating hydrolysis of chemical compounds. The surface morphology of bark did not change considerably after partial liquefaction. Particleboards with PLB in the core layers showed overall lower densities and mechanical properties (modulus of elasticity, modulus of rupture, and internal bond strength), and were less water-resistant as compared to the ones with PLB used in the surface layers. Formaldehyde emissions from the particleboards were 0.284-0.382 mg/m2·h, and thus, below the E1 class limit required by European Standard EN 13986:2004. The major emissions of volatile organic compounds (VOCs) were carboxylic acids as oxidization and degradation products from hemicelluloses and lignin. The application of PLB in three-layer particleboards is more challenging than in single-layer boards as PLB has different effects on the core and surface layers.

Alternative Materials from Agro-Industry for Wood Panel Manufacturing-A Review.

The growing demand for wood-based panels for buildings and furniture and the increasing worldwide concern for reducing the pressure on forest resources require alternatives to wood raw materials. The agricultural industry not only can provide raw materials from non-wood plants but also numerous residues and side streams. This review supplies an overview of the availability, chemical composition, and fiber characteristics of non-wood lignocellulosic materials and agricultural residues, i.e., grow care residues, harvest residues, and process residues, and their relevance for use in wood panel manufacturing. During the crop harvest, there are millions of tons of residues in the form of stalks, among other things. Usually, these are only available seasonally without using storage capacity. Process residues, on the other hand, can be taken from ongoing production and processed further. Fiber characteristics and chemical composition affect the panel properties. Alternatives to wood with long fibers and high cellulose content offer sufficient mechanical strength in different panel types. In general, the addition of wood substitutes up to approximately 30% provides panels with the required strength properties. However, other parameters must be considered, such as pressing temperature, adhesive type, press levels, and pretreatments of the raw material. The search for new raw materials for wood panels should focus on availability throughout the year, the corresponding chemical requirements and market competition. Panel type and production process can be adapted to different raw materials to fit niche products.

Polyurethane Wood Adhesives Prepared from Modified Polysaccharides.

This study investigated the performance of polyurethane adhesives prepared with various combinations of wheat starch that had been modified by isophorone diisocyanate (MS), two polyol types (1,3-propanediol (PD) and glycerol (Gly)), native wheat starch (NS), and 4,4'-diphenylmethane diisocyanate (pMDI) at a NCO:OH weight ratio of 1:1. Two more adhesives were also synthesized with NS, PD, or Gly and pMDI blends and served as controls. The thermal behavior of the adhesives before and after the curing process, as well as their rheological performance and lap shear strength, were analyzed. Differential scanning calorimetry (DSC) showed a reduction in curing temperature and heat by adding MS. The thermal stability of the cured adhesives was slightly increased by MS addition. The viscosity of the adhesives that contained MS substantially increased at a linear ascendant ramp of shear, while the controls exhibited relatively low viscosity during the whole shear rate spectrum from 0.1 to 100 s-1. The tensile shear strength of wood veneers was also significantly increased by the incorporation of MS under both dry and wet measuring conditions. The maximum dry shear strength was obtained for the adhesive with Gly polyol and a higher content of MS and was comparable to the control adhesive with pMDI.

Application of Waterborne Acrylic and Solvent-Borne Polyester Coatings on Plasma-Treated Fir (Abies alba M.) Wood.

This research investigates the effect of plasma treatment with air, nitrogen (N2), and carbon dioxide (CO2) gases on the performance of waterborne (acrylic) and solvent-borne (polyester) coated fir (Abies alba M.) wood samples. The properties of the plasma-coated samples were analyzed before and after exposure to accelerated weathering and compared with those of untreated and solely treated ones. According to pull-off testing, the coating adhesion of the wood samples was considerably improved by plasma treatment, and obvious differences were observed between different plasma gases. The effect was more pronounced after the weathering test. Similar results were obtained for the abrasion resistance of the samples. The water contact angle measurement illustrated more hydrophilic character in the solely plasma-treated wood in comparison with the untreated wood. The application of coatings, however, strongly improved its hydrophobic character. The performances of waterborne and solvent-borne coatings on plasma-treated wood were comparable, although slightly better values were obtained by the waterborne system. Our results exhibit the positive effect of plasma treatment on coating performances and the increased weather resistance of the waterborne and solvent-borne coating systems on plasma-treated wood.

Preparation of Polyurethane Adhesives from Crude and Purified Liquefied Wood Sawdust.

Polyurethane (PU) adhesives were prepared with bio-polyols obtained via acid-catalyzed polyhydric alcohol liquefaction of wood sawdust and polymeric diphenylmethane diisocyanate (pMDI). Two polyols, i.e., crude and purified liquefied wood (CLW and PLW), were obtained from the liquefaction process with a high yield of 99.7%. PU adhesives, namely CLWPU and PLWPU, were then prepared by reaction of CLW or PLW with pMDI at various isocyanate to hydroxyl group (NCO:OH) molar ratios of 0.5:1, 1:1, 1.5:1, and 2:1. The chemical structure and thermal behavior of the bio-polyols and the cured PU adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Performance of the adhesives was evaluated by single-lap joint shear tests according to EN 302-1:2003, and by adhesive penetration. The highest shear strength was found at the NCO:OH molar ratio of 1.5:1 as 4.82 ± 1.01 N/mm2 and 4.80 ± 0.49 N/mm2 for CLWPU and PLWPU, respectively. The chemical structure and thermal properties of the cured CLWPU and PLWPU adhesives were considerably influenced by the NCO:OH molar ratio.

Hydrophobic Formulations Based on Tall Oil Distillation Products for High-Density Fiberboards.

This study investigates the effect of renewable formulations based on tall oil bio-refinery products on the water vapor sorption and interfiber strength of cellulosic fibers as well as on the properties of high-density fiberboard (HDF) panels. The results obtained for HDF prepared using renewable formulations were compared to the results for HDF obtained using conventional synthetic paraffin wax (hydrowax), which is the hydrophobic agent currently utilized by the industry. Four tall oil distillation products (TODPs) with different levels of fatty and rosin acids were used for preparing the hydrophobic formulations with furfuryl alcohol as an organic solvent. According to determinations with an automated vapor sorption apparatus, the formulations had a similar effect with hydrowax on the sorption behavior of natural fibers. Unlike to hydrowax treatment, the ultimate tensile strength of cellulosic paper-sheets treated with the formulations remained unchanged or significantly increased. At the standard addition load of 1% (wt/wt dry fibers) of the formulations, HDF panels showed comparable and only in one case, e.g., TODP3-based formulation, slightly higher thickness swelling (24 h) than those with hydrowax. The best performing formulation (TODP2-based) in terms of tensile strength of paper sheets did not significantly change the mechanical properties of HDF panels in both standard climate and high humid conditions. Promising results at the standard and humid climate conditions were obtained for HDF panels manufactured with higher TODP2-based formulation amounts (3-5%) and reduced melamine-urea-formaldehyde resin content (10-12% instead of 14%, wt dry resin/wt dry fibers).

Ammonium Lignosulfonate Adhesives for Particleboards with pMDI and Furfuryl Alcohol as Crosslinkers.

Tightening formaldehyde emission limits and the need for more sustainable materials have boosted research towards alternatives to urea-formaldehyde adhesives for wood-based panels. Lignin residues from biorefineries consist of a growing raw material source but lack reactivity. Two crosslinkers were tested for ammonium lignosulfonate (ALS)-bio-based furfuryl alcohol (FOH) and synthetic polymeric 4,4'-diphenylmethane diisocyanate (pMDI). The addition of mimosa tannin to ALS before crosslinking was also evaluated. The derived ALS adhesives were used for gluing 2-layered veneer samples and particleboards. Differential Scanning Calorimetry showed a reduction of curing temperature and heat for the samples with crosslinkers. Light microscopy showed that the FOH crosslinked samples had thicker bondlines and higher penetration, which occurred mainly through vessels. Tensile shear strength values of 2-layered veneer samples glued with crosslinked ALS adhesives were at the same level as the melamine reinforced urea-formaldehyde (UmF) reference. For particleboards, the FOH crosslinked samples showed a significant decrease in mechanical properties (internal bond (IB), modulus of elasticity (MOE), modulus of rupture (MOR)) and thickness swelling. For pMDI crosslinked samples, these properties increased compared to the UmF. Although the FOH crosslinked ALS samples can be classified as non-added-formaldehyde adhesives, their emissions were higher than what can be expected to be sourced from the particles.

Modification of Pea Starch and Dextrin Polymers with Isocyanate Functional Groups.

Pea starch and dextrin polymers were modified through the unequal reactivity of isocyanate groups in isophorone diisocyanate (IPDI) monomer. The presence of both urethane and isocyanate functionalities in starch and dextrin after modification were confirmed by Fourier transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C NMR). The degree of substitution (DS) was calculated using elemental analysis data and showed higher DS values in modified dextrin than modified starch. The onsets of thermal degradation and temperatures at maximum mass losses were improved after modification of both starch and dextrin polymers compared to unmodified ones. Glass transition temperatures (Tg) of modified starch and dextrin were lower than unmodified control ones, and this was more pronounced in modified dextrin at a high molar ratio. Dynamic water vapor sorption of starch and dextrin polymers indicated a slight reduction in moisture sorption of modified starch, but considerably lower moisture sorption in modified dextrin as compared to that of unmodified ones.