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

Micro-fibrillated cellulose in lignin–phenol–formaldehyde adhesives for plywood production

Petrochemical-based phenol–formaldehyde (PF) adhesives are widely used in plywood production. To substitute phenol in the synthesis of PF adhesives, lignin can be added due to its structural similarity to phenol. Moreover, micro-fibrillated cellulose (MFC) can further enhance the bond performance, mechanical properties, and toughness of adhesive systems. Thus, the aim of this study was to evaluate the adhesion performance of lignin–PF (LPF) adhesives reinforced with MFC. In LPF formulations, three levels of MFC (0, 15, and 30 wt% based on the total solid content of adhesives) were added to the homogenous adhesive mixture. Three-layer plywood panels from birch (Betula pendula Roth.) veneers were assembled after hot pressing at 130 ◦C under two pressing durations, e.g., 60 and 75 s/mm. Tensile shear strength was measured at dry (20 ◦C and 65% RH) and wet conditions (water soaked at room temperature for 24 h). The results indicated that the addition of lignin reduced the strength of LPF adhesives in both dry and wet conditions compared to the control PF adhesive. However, MFC reinforcement enhanced the shear strength properties of the plywood. Furthermore, a longer pressing time of 75 s/mm slightly increased the shear strength

Vacuum-heat treatment of Scots pine (Pinus sylvestris L.) wood pretreated with propanetriol

Scots pine sapwood was pretreated with two levels of propanetriol (20% and 40% w/w glycerol), and then subjected to vacuum-heat treatment (VHT) at 180 degrees C and 200 degrees C. The treated samples were examined with respect to their weight and volumetric changes, mechanical properties, colour changes, and dynamic water vapour sorption. The weight of the samples after VHT did not change with increasing the temperature, but it was increased in glycerol pretreated samples. Combination of glycerol pretreatment and VHT decreased the maximum swelling. Total colour change was significantly higher during VHT at a higher temperature, while no obvious trend observed in the samples pretreated with glycerol. Modulus of elasticity (MOE) and modulus of rupture (MOR) were not affected by solely VHT, but strongly decreased after glycerol pretreatment. The equilibrium moisture content (EMC) of the samples decreased by VHT. The glycerol pretreatment caused a reduction in EMC values at a relative humidity (RH) below 60%, but considerably increased the moisture sorption in the RH above 75%. VHT slightly reduced the sorption hysteresis compared to untreated wood, but an apparent reduction in hysteresis observed by glycerol pretreatment. This indicates that the flexibility of the wood cell wall polymers increases due to glycerol pretreatment, which results in decreased MOE and sorption hysteresis values

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

Characterization of Wood‑based Industrial Biorefinery Lignosulfonates and Supercritical Water Hydrolysis Lignin

Understanding the properties of any particular biorefinery or pulping residue lignin is crucial when choosing the right lignin for the right end use. In this paper, three different residual lignin types [supercritical water hydrolysis lignin (SCWH), ammonium lignosulfonate (A-LS), and sodium lignosulfonate (S-LS)] were evaluated for their chemical structure, thermal properties and water vapor adsorption behavior. SCWH lignin was found to have a high amount of phenolic hydroxyl groups and the highest amount of beta-O-4 linkages. Combined with a low ash content, it shows potential to be used for conversion into aromatic or platform chemicals. A-LS and S-LS had more aliphatic hydroxyl groups, aliphatic double bonds and C=O structures. All lignins had available C-3/C-5 positions, which can increase reactivity towards adhesive precursors. The glass transition temperature (T-g) data indicated that the SCWH and S-LS lignin types can be suitable for production of carbon fibers. Lignosulfonates exhibited considerable higher water vapor adsorption as compared to the SCWH lignin. In conclusion, this study demonstrated that the SCWH differed greatly from the lignosulfonates in purity, chemical structure, thermal stability and water sorption behavior. SCWH lignin showed great potential as raw material for aromatic compounds, carbon fibers, adhesives or polymers. Lignosulfonates are less suited for conversion into chemicals or carbon fibers, but due to the high amount of aliphatic hydroxyl groups, they can potentially be modified or used as adhesives, dispersants, or reinforcement material in polymers. For most value-adding applications, energy-intensive purification of the lignosulfonates would be required.Open access funding provided by Linnaeus University. Venla Hemmila and Stergios Adamopoulos would like to thank the Knowledge Foundation for the financial support (project titled "New environment-friendly board materials", 2015-2019). Arantxa Eceiza thanks the Basque Government (IT776-16) and SgiKer General Services of the University of the Basque Countr

Anatomical, physical, chemical, and biological durability properties of two rattan species of different diameter classes

Rattan cane is an important forest product with economic value. Its anatomical, physical, and biological properties vary with the cane height. This makes it difficult to select the appropriate cane diameter for harvesting. Understanding the material properties of rattan cane with different diameter sizes is important to enhance its utilization and performance for different end uses. Thus, the present study was performed on two rattan species, Calamus zollingeri and Calamus ornatus, at two different cane heights (bottom/mature and top/juvenile). Calamus zollingeri was studied at diameter classes of 20 mm and 30 mm, while Calamus ornatus was analyzed at a diameter class of 15 mm. The anatomical properties, basic density, volumetric swelling, dynamic moisture sorption, and biological durability of rattan samples were studied. The results showed that C. zollingeri with a 20 mm diameter exhibited the highest basic density, hydrophobicity, dimensional stability, and durability against mold and white-rot (Trametes versicolor) fungi. As confirmed by anatomical studies, this could be due to the higher vascular bundle frequency and longer thick-walled fibers that led to a denser structure than in the other categories. In addition, the lignin content might have a positive effect on the mass loss of different rattan canes caused by white-rot decay

Chemical composition, particle geometry, and micro-mechanical strength of barley husks, oat husks, and wheat bran as alternative raw materials for particleboards

Particleboards are used worldwide in various industry segments, like construction and furniture production. Nevertheless, increase in wood prices and logistical challenges urge the particleboard industry to find alternative raw materials. By-products and residues from the agricultural and food industries could offer possibilities for material sourcing at a local level. This study aimed to investigate the chemical composition, particle geometry, anatomical structure, and microtensile characteristics of such material, specifically barley husks (BH), oat husks (OH), and wheat bran (WB). BH and OH were found to have comparable hemicelluloses and lignin contents to industrial wood chips but contained more ash. WB was rich in extractives and showed high buffering capacity. Light microscopy and microcomputed tomography revealed details of leaf structure for BH and OH as well as the multi-layer structure of WB. The ultimate microtensile strength of BH, various OH samples, and WB were respectively 2.77 GPa, 0.84–2.42 GPa, and 1.45 GPa. The results indicated that the studied materials could have potential uses as furnish materials in non-load bearing particleboards, where thermal or acoustic insulation properties are desirable

Preparation of polyurethane adhesives from crude and purified liquefied wood sawdust

Polyurethane (PU) adhesives were prepared with bio-polyols obtained via acid-catalyzedpolyhydric alcohol liquefaction of wood sawdust and polymeric diphenylmethane diisocyanate(pMDI). Two polyols, i.e., crude and purified liquefied wood (CLW and PLW), were obtained fromthe 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 thebio-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 singlelap joint shear tests according to EN 302-1:2003, and by adhesive penetration. The highest shearstrength 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. Södra Stiftelse: Bio-based polyurethane adhesives for cross-laminated timber (CLT)Formas project 942-2016-2, 2017-2

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 C-13 nuclear magnetic resonance (C-13 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 (T-g) 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.Reza Hosseinpourpia and Stergios Adamopoulos thank VINNOVA, Swedish Governmental Agency for Innovation Systems (VINNMER Marie Curie Incoming project, grant No. 2015-04825). Arantzazu Santamaria-Echart and Arantxa Eceiza wish to acknowledge the financial support from the Basque Government in the frame of Grupos Consolidados (IT-776-13) and SGIker from the University of the Basque Country for their Technical support

Degradation assessment of archaeological oak (Quercus spp.) buried under oxygen-limited condition

The biological deterioration of archaeological wood under oxygen-limited conditions varies due to the limited activities of microorganisms. It is essential to expand the knowledge of the degradation types and the status of archaeological monuments for selecting the proper consolidates. The physical, chemical, and anatomical properties of approximately 600-650 year old archaeological oak collected from an archaeological site in Iasi-Romania were analysed to assess the quality and to identify the degradation types. The results were compared with similar tests on recently-cut oak. X-ray photoelectron spectroscopy (XPS) revealed the presence of more lignin-related peaks in the archaeological oak, which likely reflected the degradation of the wood carbohydrates as evidenced by the decreased oxygen-to-carbon ratio Cox/Cnon-ox. The differences in cellulose crystallinity were not significant suggesting that any cellulose degradation occurred in the amorphous regions. This was also reflected in the dynamic water vapor sorption analysis where the differences in sorption isotherms and hysteresis of archaeological and recently-cut oaks were marginal. Microscopic analysis of the oak cells illustrated bacterial degradation patterns, while the field emission scanning electron microscopy (FESEM) showed the presence of erosion bacteria in the archaeological oak collected from the site with low oxygen conditions