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Lignin was successfully modified to prepare a bio-based wood adhesive by just two synthesis steps: demethylation and periodate oxidation. Fourier Transform Infrared Spectroscopy (FT-IR), Matrix Assisted Laser Desorption Ionization Time of Flight (MALDI-TOF) Mass Spectrometry and Thermomechanical Analysis (TMA) were combined to characterize the bio-based adhesives obtained. Furthermore, the adhesion performance of the bio-based lignin adhesive was measured by testing the tensile shear strength of the bonded joints. The results show that demethylated lignin gives to the wood joint acceptable dry shear strength, but no wet shear strength. Thus, sodium peroxide (NaIO4) oxidant was used to improve the bonding performance of lignin-based adhesives. The optimal formulation for oxidized demethylated lignin adhesives was found to be by 20% addition of NaIO4. The adhesive presented is a lignin-derived non- aldehyde addition, high biomass content, and its preparation is convenient, low-cost product and can be applied to wood bonding.

To prepare a natural tannin-based adhesive with good water resistance, an environment friendly furfuryl alcohol-glyoxal resin (FG) synthesized in the laboratory was developed as a cross-linker for tannin-based adhesives. 13C Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption-Ionization Time-of-Flight (MALDI-TOF) mass spectroscopy results indicated that furfuryl alcohol and glyoxal reacted under acidic conditions and that the -CH-(OH)- groups could be shown to be the ones involved in the cross-linking of the tannin-furfuryl-glyoxal adhesive (TFG). The results for the wet shear strength of TFG-bonded plywood showed that the cured TFG was improved and better than that bonded with a tannin-furfuryl alcohol (TF) adhesive. Moreover, the TFG adhesive cross-linked with 12% epoxy resin (EPR) presented a good water resistance. It had a modulus of elasticity (MOE) higher than that of tannin-furfuryl alcohol-formaldehyde (TFF), TF and phenol-formaldehyde (PF) adhesives.

Understanding the interfacial changes of wood during heat treatment can facilitate the improvement of the bonding and coating processes of heat-treated wood. Steam was used as the medium to modify Pinusmassoniana wood through heat treatment at 160, 180, 200, and 220 °C. Changes to the surface characteristics after heat treatment were characterized by Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscope (SEM) and contact angle measurement. The results showed that: (1) hemicelluloses were the first to experience degradation at 160 °C, and this degradation was the most intense at 200 °C. The cellulose started experiencing obvious degradation at 200 °C, while there was less degradation of lignin at this temperature. (2) Oxygen-containing groups like hydroxyl and carbonyl were gradually reduced as temperature increased with deepened color and passivated surface. (3) Cellulose crystallinity presented a variable trend of increasing–decreasing–increasing. (4) Surface porosity and roughness of Pinus massoniana wood both increased after heat treatment. (5) The Pinus massoniana wood interface turned from hydrophilic to hydrophobic, and 180 °C was a turning point for the wettability of the Pinus massoniana wood interface.

International audience; Soy-protein isolate (SPI) was used to prepare non-isocyanate polyurethane (NIPU) thermosetting adhesives for wood panels by reacting it with dimethyl carbonate (DMC) and hexamethylene diamine. Both linear as well as branched oligomers were obtained and identified, indicating how such oligomer structures could further cross-link to form a hardened network. Unusual structures were observed, namely carbamic acid-derived urethane linkages coupled with lactam structures. The curing of the adhesive was followed by thermomechanical analysis (TMA). It appeared to follow a two stages process: First, at a lower temperature (maximum 130°C), the growth of linear oligomers occurred, finally forming a physically entangled network. This appeared to collapse and disentangle, causing a decrease of MOE, as the temperature increases. This appears to be due to the ever more marked Brownian movements of the linear oligomer chains with the increase of the temperature. Second, chemi- cal cross-linking of the chains appeared to ensue, forming a hardened network. This was shown by the thermo- mechanical analysis (TMA) showing two distinct MOE maxima peaks, one around 130°C and the other around 220°C, with a very marked MOE decrease between the two. Plywood panels were prepared and bonded with the SPI-NIPU wood adhesive and the results obtained are presented. The adhesive appeared to pass comfortably the requirements for dry strength of relevant standards, showing to be suitable for interior grade plywood panels. It did not pass the requirements for wet tests. However, addition of 15% of glycerol diglycidyl ether improved the wet tests results but still not enough to satisfy the standards requirements.

International audience; Wheat gluten protein hydrolysate was used as a biomass feedstock to prepare environmentally friendly protein-based adhesives, with hydrolyzed wheat protein as control. Glutaraldehyde was used to modify it to obtain a glutaraldehyde-wheat protein (GP) adhesive. Polyethylenimine (PEI) was also used as a crosslinking agent. Plywood has been prepared and tested, and its performance was used to measure the wheat gluten protein hydrolysate adhesive bonding performance. Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to analyze the adhesive thermal properties and the microstructures of the cured adhesives by scanning electron microscopy (SEM). The results show that modification by glutaraldehyde can effectively improve the bonding performance of wheat protein adhesives, the plywood bonded strength having been improved by its addition. The effect of PEI as a crosslinking agent became evident. It can greatly improve the bonding properties of glutaraldehyde-modified wheat protein adhesives. TMA analysis indicates that the glutaraldehydemodified GP adhesive has a higher storage modulus than the unmodified one. The modulus of the adhesive increased after adding the PEI cross-linking agent.

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Glyoxal as a nonvolatile and nontoxic aldehyde, which can be used as a substitution of formaldehyde in wood industry to prepare novel melamine-glyoxal (MG) resins. However, for the reason of the lo...

Furfuryl alcohol, a biosourced material, is widely used in the foundry industry, and also as additive or modifier in the adhesives field. However, furanic resins have not been reported as being use...

Broussonetiapapyrifera leaf protein was used as a biomass feedstock to prepare wood adhesives, and the influence of cutting modes (cutting frequencies and cutting heights) on leaf protein content and reactivity was studied in this paper. Bonding performance of Broussonetiapapyrifera leaf protein-based adhesives were evaluated by shear strength of plywood. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetry (TG), and scanning electron microscope (SEM) were used to analyze them. The results indicated that: (1) the leaf protein content gradually increased as the cutting height increased, but it presented a decreasing trend as the cutting frequency increased. When the cutting frequency is two times per year and the cutting height is 30 cm, this leaf protein-based adhesive exhibited the best bonding strength with 0.75 MPa. (2) Cutting frequency and cutting height have no significant correlations to the reactivity of leaf protein with the crosslinker. (3) DSC and FTIR indicated that both leaf protein content and reactivity appeared to exert an influence on the bonding properties of the protein adhesives, and the latter is more pronounced. (4) TG and SEM analyses indicated that under different cutting modes, leaf protein content, especially protein reactivity, had a great effect on the thermal properties of the adhesives. (5) Contact angle analysis showed that Broussonetiapapyrifera leaf protein-based adhesives had good wettability on wood surfaces. Under different cutting modes with the difference of leaf protein content and reactivity, the crosslinking degree of the adhesives with crosslinker and compactness of the cured adhesives were different and thus affect their bonding strength and water resistance.

By using only glyoxal instead of formaldehyde to prepare environment-friendly amino resin for wood adhesives is a hot topic in the wood industry. However, the existing reports on UG resin present a poor bonding performance, and especially an almost complete absence of water resistance. Thus, to explore new synthetic processes to prepare UG resins with good water resistance is a work of considerable interest. In this work a novel formulation is developed by reacting hexamethylene diamine (H) and urea (U) via first deamination and then polymerization with glyoxal (G) to obtain HUGs green resins. These resins were used to prepare well bonded wood panels. The effect of different H/U ratios on resin performance was also investigated. At a H/U molar ratio of 1, the HUG resin presents the best performance, dry strength, 24h wet strength, and 63℃ hot water soaking wet strength of the plywood bonded with it, these being respectively 1.18MPa, 1.70MPa, 0.92MPa respectively. This means that the HUG resin has potential as an industrial adhesive to replace urea-formaldehyde or melamine-urea- formaldehyde resins in the production of wood composites.

Chitosan is a biomass material with abundant reserves. It has been used in this work to prepare an environmentally friendly wood adhesive. By employing carbohydrates, namely glucose, sucrose and starch modified by specific oxidation as hardeners, petroleum-based aldehydes were eliminated due to their unsustainability, volatility, and toxicity. Three-layer laboratory plywood was prepared to measure the bonding performance of the chitosan adhesives prepared. The effect of different levels of oxidation by different sodium periodate additions on their bonding performance was also studied. The thermal properties of the chitosan adhesives were analyzed by differential scanning calorimetry (DSC) and thermomechanical analysis (TMA). Fourier-transform infrared (FTIR) spectrometry and matrix assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry were used to explain the reaction mechanisms involved. Oxidized carbohydrates have been shown to effectively improve the bond strength and water resistance of chitosan adhesives, with oxidized starch showing a better improvement than glucose and sucrose. The best chitosan-oxidized starch (CS) adhesive is obtained by treatment with 8 mass% of oxidized starch mixed with a chitosan solution at ambient temperature, when 10% sodium periodate on starch weight is used for its specific oxidation. Thermal analysis shows that the chitosan-oxidized starch (CS) adhesive cures at a lower temperature than the other adhesives in this work, this being one of the reasons for CS having a better bonding performance. MALDI and FTIR showed oxidized glucose, taken as a model, to form aldehydes and condensation products due to water elimination between two aldehyde groups, followed then by their reaction with the chitosan.

A partially biobased self-blowing and self-hardening polyurethane foam from glucose-based non-isocyanate polyurethanes (g-NIPU) was prepared by reaction of glucose with dimethyl carbonate and hexamethylene diamine. However, these foam types generally require a high foaming temperature. In this paper, a self-blowing foam based on g-NIPU was prepared at room temperature by using maleic acid as an initiator and glutaraldehyde as a crosslinker. Water absorption, compression resistance, and fire resistance were tested. Scanning electron microscopy (SEM) was used to observe the foam cells structure. Middle infrared (ATR FT-MIR) and Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) mass spectrometry were used to help to analyze the reactions during the foaming process. The results obtained showed that self- blowing rigid foams have good compression, this being directly proportional to the foam density. Increasing the amount of glutaraldehyde or reducing maleic acid thickens the cell walls and increases the density of the foams. MALDI-TOF analysis showed that g-NIPU reacts with both maleic acid and glutaraldehyde. The foams presented poor fire resistance indicating that, as for isocyanate based polyurethane foams, addition of a fire retardant would be necessary.

Sucrose-based non-isocyanate polyurethanes (S-NIPU) were synthesized by the already codified reaction of sucrose, dimethyl carbonate and hexamethylene diamine and used for the first time as adhesives for bonding particleboard. To decrease the NIPU adhesive curing temperature, a silane coupling agent was used as a crosslinking promoter. The performance of particleboards prepared at a press temperature of 230 °C, 200 °C and 180 °C and a press time of 8 min, 10 min and 12 min was tested and evaluated. The structure of the oligomers obtained was detected by matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Thermomechanical analysis and differential scanning calorimetry were also used to analyze their behavior. The particleboards bonded with the S-NIPU adhesive at 230 °C showed excellent properties, which, however, decreased as the press time was reduced. The silane coupling agent used as a crosslinking promoter significantly reduced the curing temperature of the adhesive and allowed to obtain good bonding at a lower press temperature. The results obtained confirmed that coupling the S-NIPU adhesive with a silane used as a crosslinking promoter can yield sufficiently improved results to function as a suitable adhesive for particleboard, medium density fiberboard and other types of particulate wood panels. It was also the first time that a NIPU adhesive was used for wood bonding.

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(1) A compound protectant was prepared using manganese chloride, phosphoric acid, boric acid and ammonium chloride, and then a veneer was immersed in the prepared protectant to prepare plywood in this paper. Great attention was paid to discussing influences of such protectant on fire resistance, decay resistance, anti-mold property and bonding performance of plywood. Results demonstrated that after protectant treatment, the plywood showed not only good fire resistance and smoke inhibition, but also strong char-formation ability, slow flame spreading, long time to ignition, small fire risk and high safety level. (2) The mass loss rates of plywood with protectant treatment after infection and erosion in wood-destroying Coriolus versicolor and Gloeophyllum trabeum were 19.73% and 17.27%, reaching the II-level corrosion grade. (3) There is not a significant difference with Aspergillus niger V., however, it was possible to observe a strong difference with Trichoderma viride Pers. ex Fr., indicating that the protectant acted as a good anti-mold product for plywood. (4) The protectant influenced the bonding interface of wood and bonding conditions of the adhesive. The bonding strength of plywood was weakened, but it still met the requirements on bonding strength of GB/T 9846-2015. (5) The protectant changed the thermal decomposition and thermal degradation of plywood, inhibiting the generation of inflammable goods, blocking transmission of heats and lowering the thermal decomposition temperature of plywood. These promoted dehydrations and charring of wood and the generated carbon had a high thermal stability. (6) Compared with untreated plywood, the prepared protectant treatment significantly enhanced the fire resistance of plywood, reduced its biodegradability by wood-decaying fungi and showed good mold resistance.

The characteristics of UF resin prepared with concentrated formaldehyde were studied in this paper. With the molar ratio F/U = 1.1, the UF resin prepared with concentrated formaldehyde showed better mechanical properties than that with formalin. The 13C-NMR and FTIR results indicated that there were more methylene groups, ether groups and urons in a UF resin system prepared with concentrated formaldehyde than those in a normal UF resin. The differential scanning calorimetry and DMA results showed that the curing temperature of UF resin with concentrated formaldehyde was lower than that of a normal UF resin. UF resin with concentrated formaldehyde showed worse thermal stability and higher thermal decomposition temperature.

To develop a soy-based adhesive with good water resistance, non-toxic melamine–glyoxal resin (MG) prepared in the laboratory was used as a cross-linker of soy-based adhesive. The FT-IR and ESI-MS results showed that there was a reaction between melamine and glyoxal. The resulted –CH–OH– groups could be the possible reactive groups for the cross-linking of soy-based adhesive. The wet shear strength of soy-based plywood indicated that the water resistance of soy adhesive cross-linked by MG improved with respect to that with no cross-linker, although it was not good enough to satisfy the relative standard. With the optimized preparation procedures for plywood, specifically, press temperature 180 °C, press time 3 min and resin loading 280 g m−2, type I soy-based plywood could be prepared with a hybrid cross-linker, namely 12%MG + 2% epoxy resin (EPR). The DSC results showed that the reaction between soy-based adhesive and the hybrid cross-linker MG + EPR was very complex.

Sodium periodate has been shown to cleave glucose by specific oxidation to yield a number of non-volatile aldehydes which can react with the phenolic compounds in tannin extract and lead to tannin cross-linking and hardening. This approach to prepare a tannin resin useable for wood adhesives can be used by either treating with periodate a mixture of tannin and glucose, or to treat glucose beforehand with periodate to cleave it and generate the aldehydes, and only afterwards to mix it with the tannin. The results obtained with these two methods are identical, but the latter method avoids oxidation of tannin. The aldehydes were generated either by direct cleavage of glucose C–C bonds carrying vicinal oriented hydroxyls, or by recombination of the aldehydes so formed by aldol condensation or by water elimination between two aldehyde groups. MALDI ToF analysis indicated that all the three types of aldehydes appeared to react with the polyphenols in the tannin. Thermomechanical analysis (TMA) and plywood bonded with the tannin + glucose + periodate mixes gave good bonding results, with dry, 24 h cold water soaking and 3 h at 63 °C shear strength values improving concomitantly to the proportion of periodate used for the oxidation step.

Ambient temperature self-blowing mimosa tannin-based non-isocyanate polyurethane (NIPU) rigid foam was produced, based on a formulation of tannin-based non-isocyanate polyurethane (NIPU) resin. A citric acid and glutaraldehyde mixture served as a blowing agent used to provide foaming energy and cross-link the tannin-derived products to synthesize the NIPU foams. Series of tannin-based NIPU foams containing a different amount of citric acid and glutaraldehyde were prepared. The reaction mechanism of tannin-based NIPU foams were investigated by Fourier Trasform InfraRed (FT-IR), Matrix Assisted Laser Desorption Ionization (MALDI-TOF) mass spectrometry, and 13C Nuclear Magnetic Resonance (13C NMR). The results indicated that urethane linkages were formed. The Tannin-based NIPU foams morphology including physical and mechanical properties were characterized by mechanical compression, by scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). All the foams prepared showed a similar open-cell morphology. Nevertheless, the number of cell-wall pores decreased with increasing additions of glutaraldehyde, while bigger foam cells were obtained with increasing additions of citric acid. The compressive mechanical properties improved with the higher level of crosslinking at the higher amount of glutaraldehyde. Moreover, the TGA results showed that the tannin-based NIPU foams prepared had similar thermal stability, although one of them (T-Fs-7) presented the highest char production and residual matter, approaching 18.7% at 790 &deg, C.

By using renewable inexpensive plant-derived materials such as lignin and furfuryl alcohol, a new bio-based, easily-prepared, and industrially suitable thermosetting grinding wheel named lignin-furanic grinding wheel (LFG) was prepared and characterized. Cross-linking between lignin and furfuryl alcohol under acidic conditions was established by carbon-13 nuclear magnetic resonance (13C-NMR) and electrospray ionization mass spectrometry (ESI-MS). In addition, as the results of thermomechanical analysis (TMA) and thermogravimetric analysis (TGA) suggested, the lignin-furanic resin exhibited high resistance to heat, and the glass transition temperature (Tg) as high as 170 °C. The new lignin-based grinding wheel presented no pores or cracks in the surface and it had a high hardness and compression resistance compared to the commercial phenolic grinding wheel (PG). Moreover, it exhibited high abrasiveness, and the cutting time for a metal tube was shorter than that of PG.

To improve the water resistance of soy-based adhesive for wood panels, three kinds of cross-linkers, namely, epoxy resin (EPR), melamine–formaldehyde (MF) and their mixture EPR+MF were used in this paper. The results indicated that all the three cross-linkers improved the water resistance of soy-based adhesive and the hybrid cross-linker EPR+MF, was the best. With press temperature 160 °C and press time 8 min, type II and even type I plywood could be prepared when 6.4%EPR+6.4%MF is used as cross-linker of soy-based adhesive. FT-IR indicated that the great improvement of water resistance of soy-based adhesive modified with EPR and MF might be caused by the reaction between epoxy and –OH, and that between MF and –NH.

To prepare a low-formaldehyde soy-based adhesive with good water resistance, phenol-formaldehyde modified with glutaraldehyde (PFG) with lower free phenol and free formaldehyde contents was used to cross-link the soy-based adhesive. The results showed that the mechanical properties and water resistance of plywood prepared with soy-based adhesive with PFG was better than that of plywood with the same amount of phenol-formaldehyde (PF). The reaction between phenol and glutaraldehyde was proved by 13C-NMR. Under the optimized preparation conditions for plywood, that is to say, press temperature 160 °C, press time 4 min and resin loading 320 g·m−2, type I plywood could be prepared with 9% PFG as a cross-linker of soy-based adhesive. The Differential Scanning Calorimetry (DSC) result confirmed the cross-linking reaction between soy-based adhesive and PFG or PF. The activation energy of soy-based adhesive with cross-linker PFG was higher than that with PF resin.