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In this study, cross-bonded self-binding and bone glue-bonded particleboards were manufactured from sugarcane (Saccharum officinarum L.) bagasse with different pre-treatments of particles. Six types of panels were manufactured from bagasse particles with and without bone glue. The physical, mechanical, and thermal properties of the panels were examined according to the standards. Fourier Transform Infrared (FTIR) spectroscopy and thermogravimetric analysis (TG) were performed to investigate the changes in the chemical bonds and thermal stability of the fabricated composites, respectively. It was found that cross-bonded bagasse self-binding (TC) and bone glue-bonded (T3) panels fabricated from non-boiled bagasse particles showed higher physical and mechanical properties compared to the other types of panels. Non-boiled bagasse particles with bone glue panels showed the highest mechanical properties, i.e., modulus of rupture (MOR = 26.22 MPa), modulus of elasticity (MOE = 4302 MPa), tensile strength = 8.35 MPa, and hardness = 1.72 MPa. TC and T3 panels also showed higher thermal stability compared to the other types of panels. A new peak at 3331–3334 cm−1 for the NH stretching vibration in the FTIR analysis represents the presence of bone glue in the cross-bonded particleboards. Thus, this research advances the production of formaldehyde-free bagasse particleboard, introducing the cross-bonding technique and sustainable bone glue.

The preparation and application of non-isocyanate polyurethane (NIPU) from biomass raw materials as a substitute for traditional polyurethane (PU) has recently become a research hot topic as it avoids the toxicity and moisture sensitivity of isocyanate-based PU. In the work presented here, self-blowing GNIPU non-isocyanate polyurethane (NIPU) rigid foams were prepared at room temperature, based on glucose, with acids as catalysts and glutaraldehyde as a cross-linker. The effects of different acids and glutaraldehyde addition on foam morphology and properties were investigated. The water absorption, compressive resistance, fire resistance, and limiting oxygen index (LOI) were tested to evaluate the relevant properties of the foams, and scanning electron microscopy (SEM) was used to observe the foams’ cell structure. The results show that all these foams have a similar apparent density, while their 24 h water absorption is different. The foam prepared with phosphoric acid as a catalyst presented a better compressive strength compared to the other types prepared with different catalysts when above 65% compression. It also presents the best fire resistance with an LOI value of 24.3% (great than 22%), indicating that it possesses a good level of flame retardancy. Thermogravimetric analysis also showed that phosphoric acid catalysis slightly improved the GNIPU foams’ thermal stability. This is mainly due to the flame-retardant effect of the phosphate ion. In addition, scanning electron microscopy (SEM) results showed that all the GNIPU foams exhibited similar open-cell morphologies with the cell pore sizes mainly distributed in the 200–250 μm range.

In this study, we used a self-neutralizing system to counteract too acidic a pH, unsuitable for wood adhesives, and tested it on MUF resins augmented by the addition of citric acid or other organic acids, based on the addition of small percentages of hexamine or another suitable organic base to form an acid–base buffer. In this manner, the pH of the adhesive was maintained above the minimum allowed value of 4, and the strength results of wood particleboard and plywood bonded with this adhesive system increased due to the additional cross-linking imparted by the citric acid. Thus, the wood constituents at the wood/adhesive interface were not damaged/degraded by too low a pH, thus avoiding longer-term service failure of the bonded joints. The addition of the buffering system increased the strength of the bondline in both the plywood and particleboard, both when dry and after hot water and boiling water tests. The IB strength of the particleboard was then increased by 15–17% when dry but by 82% after boiling. For the plywood, the shear strengths when dry and after 3 h in hot water at 63 °C were, respectively, 37% and 90% higher than for the control. The improvement in the bonded panel strength is ascribed to multiple reasons: (i) the slower, more regular cross-linking rate due to the action of the buffer; (ii) the shift in the polycondensation–degradation equilibrium to the left induced by the higher pH and the long-term stability of the organic buffer; (iii) the additional cross-linking by citric acid of some of the MUF resin amine groups; (iv) the already known direct linking of citric acid with the carbohydrates and lignin constituents at the interface of the wood substrate; and (v) the likely covalent linking to the interfacial wood constituents of the prelinked MUF–citric acid resin by some of the unreacted citric acid carboxyl groups.

Soybean meal (SM) adhesive is widely acknowledged as a viable substitute for traditional formaldehyde-based adhesives, given its ability to be easily modified, the utilization of renewable sources, and its eco-friendly characteristics. However, the application of SM adhesive in manufacturing has been impeded due to its restricted bonding capacity and inadequate water resistance. Researchers in the wood industry have recognized the significance of creating an SM-based adhesive, which possesses remarkable adhesive strength and resistance to water. This study endeavors to tackle the issue of inadequate water resistance in SM adhesives. Sodium lignosulfonate (L) was oxidized using hydrogen peroxide (HP) to oxidized lignin (OL) with a quinone structure. OL was then used as a modifier, being blended with SM to prepare SM-based biomass (OLS) adhesives with good water resistance, which was found practically through its utilization in the production of plywood. The influence of the HP dosage and OL addition on plywood properties was examined. The changes in the lignin structure before and after oxidation were confirmed using gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The curing behavior and thermal stability of OLS adhesives were analyzed using dynamic mechanical analysis (DMA) and thermogravimetric (TG) analysis. The reaction mechanism was also investigated using FT-IR and XPS. The outcomes indicated a decrease in the molecular weight of L after oxidation using HP, and, at the same time, quinone and aldehyde functionalized structures were produced. As a result of the reaction between the quinone and aldehyde groups in OL with the amino groups in SM, a dense network structure formed, enhancing the water resistance of the adhesive significantly. The adhesive displayed exceptional resistance to water when the HP dosage was set at 10% of L and the OL addition was 10% based on the mass of SM. These specific conditions led to a notable enhancement in the wet bonding strength (63 °C, 3 h) of the plywood prepared using the adhesive, reaching 0.88 ± 0.14 MPa. This value represents a remarkable 125.6% increase when compared to the pure SM adhesive (0.39 ± 0.02 MPa). The findings from this study introduce a novel approach for developing adhesives that exhibit exceptional water resistance.

A thermoset polyamide resins were synthesized by citric acid and hexanediamine (CH), and was modified by oxidized glucose (OG). The effect of oxidation time and addition amount of oxidized glucose on shearing strength of plywood were characterized. Fourier transform-infrared (FT-IR) and liquid chromatography-mass spectrometry (LCMS) were used to determine the structures of the resins, the result shows that CH and OG reacted to form macromolecules. Differential Scanning Calorimeter (DSC), dynamic mechanical properties (DMA) were used to analyze its thermal properties, the results indicate that OG improved the storage module and the heat resistance. The CHOG resin exhibited a good bonding strength and water resistance, when the oxidation time is 0 min and the molar ratio of oxidized glucose to hexamethylene diamine is 1:1.6. Dry strength, 24 h wet strength and 63 °C hot water soaking wet strength of the plywood bonded with it are 1.36 MPa, 1.60 MPa, 1.49 MPa, respectively. Therefore, OG enhanced the shearing properties, and improve water resistance, which sheds new light on the preparation of bio-based wood adhesive for the manufacture of plywood.

Rosin has a great influence on the bonding of Pinus massoniana wood, and surface modification is an important way to solve this problem. In this study, Pinus massoniana wood was treated by plasma, and the effects of plasma treatment on the bonding performance and surface characteristics were investigated. The results showed the following: (1) After plasma treatment, the contact angle of Pinus massoniana wood was significantly reduced and the surface energy was significantly increased from 28.42 × 10−7 to 74.75 × 10−7 J·cm−2, and the surface wettability was also greatly improved. (2) Plasma high-energy particles experience simultaneous physical and chemical effects on the surface of Pinus massoniana wood. The former formed a micro-etched roughness on the wood surface and led to the increase in surface dispersion force, while the latter increased the aggregation and activity of polar groups on the wood surface and the degradation of some wood components and rosin, resulting in the increase in surface polar force and the enhancement of wettability. (3) After plasma treatment, the reactivity of wood was enhanced, and the cross-linking degree with adhesive and the heat release were increased. The bonding strength of Pinus massoniana wood could be improved: dry bonding from 5.08 to 5.38 MPa, boiling-water bonding strength from 4.12 to 4.53 MPa, cold-water bonding strength from 3.84 to 4.51 MPa, and the bonding stability and reliability of glued specimens were also improved.

Condensed tannin copolymerized with hyperbranched tris(2-aminoethyl)amine-urea formed by amine-amido deamination yields a particleboard thermosetting adhesive without any aldehydes satisfying the requirements of relevant standards for the particleboard internal bond strength. The tannin–triamine–urea cures well at 180 °C, a relatively low temperature for today’s particleboard hot pressing. As aldehydes were not used, the formaldehyde emission was found to be zero, not even in traces due to the heating of wood. The effect is ascribed to the presence of many reactive sites, such as amide, amino, and phenolic groups belonging to the three reagents used. The tannin appears to function as an additional cross-linking agent, almost a nucleating agent, for the triamine–urea hyperbranched oligomers. Chemical analysis by MALDI ToF and 13C NMR has shown that the predominant cross-linking reaction is that of the substitution of the tannin phenolic hydroxyls by the amino groups of the triamine. The reaction of tannin with the still-free amide groups of urea is rather rare, but it may occur with the rarer tannin flavonoid units in which the heterocyclic ring is opened. Due to the temperature gradient between the surfaces and the board core in the particleboard during hot pressing, the type and the relative balance of covalent and ionic bonds in the resin structure may differ in the surfaces and the board core.

Glyoxal is considered to be the most likely substitute for formaldehyde to synthesize resin adhesives for wood bonding due to its reactivity, structural characteristics, being non-toxic, low volatility, and acceptable cost. Regrettably, the performance of the resin synthesized using glyoxal to directly replace all formaldehyde is not totally satisfactory, especially as it has almost no water resistance. This makes such a simple alternative fail to be suitable for industrial production. To prepare an environment-friendly glyoxal-based adhesive with good bonding performance, the work presented here relies first on reacting citric acid and hexamethylene diamine, producing a polyamide, with glyoxal, and then crosslinking it, thus synthesizing a thermosetting resin (namely CHG) adhesive and applying it for plywood bonding. The plywood prepared exhibits excellent dry and wet shear strength, which are better than GB/T9846-2015 standard requirements (≥0.7 MPa), and even after being soaked in hot water at 63 °C for 3 h, its strength is still as high as 1.35 MPa. The CHG resin is then potentially an adhesive for industrial application for replacing UF (urea-formaldehyde) and MUF (melamine-urea-formaldehyde) adhesives for wood composites.

Synthetic foams have become an essential industrial product for a great variety of applications. Furfuryl alcohol, as a biomass chemical, was reacted with glyoxal at room temperature to prepare furanic-glyoxal rigid foams, and p-toluenesulfonic acid was used as a catalyst to initiate the reaction. Foams with different molar ratios (furfuryl alcohol/glyoxal) were prepared in this work, and uniform cells foams have been obtained. Their compression resistance, 24-h water absorption, density, and other basic properties were tested. Scanning electron microscopy (SEM) was used to observe the cellular morphology of the foams prepared, thermogravimetric analysis (TGA) helped to understand their thermal and combustion properties, and FTIR and Matrix Assisted Laser Desorption Ionisation Time of Flight (MALDI ToF) mass spectroscopy to explain the structure of the resulting foams to clarify the reactions occurring during foaming. The results show that the compression resistance of furanic-glyoxal foams declined as the furfuryl alcohol/glyoxal ratio decreases also. SEM observations revealed that foams with open-cell were obtained when furfuryl alcohol was added in greater amounts, and more closed cell structures were formed as the proportion of glyoxal increased. TGA results showed that the initial ignition temperature of furanic-glyoxal foams is ~200 °C higher than that of wood, and the smaller comprehensive combustion index S (about 0.15 × 10−7 (%2 K−3 min−2)) indicates that the foam burns slowly and has poor flammability, that is, it is not easy to burn.

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 °C.

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.

Soy protein isolate (SPI) and insoluble soy flour polymeric carbohydrates have been reacted with sodium periodate for the specific oxidation of vicinal −OH groups to investigate the reactions involved in this approach to soy flour adhesives. The reactions have been shown to generate carbohydrate oligomer fractions presenting one, two or multiple aldehyde groups. With the exception of the small molecular weight heptanedial, the smaller molecular weight aldehydes generated from mono- and disaccharides by the same reaction do not appear to form from the insoluble soy flour carbohydrates, or have already reacted. The reaction of periodate with soy protein isolate has been shown to generate some aldehydes too. When the mix of SPI and soy insoluble carbohydrates is treated with periodate, the majority of the observed aldehyde carrying species appear to be higher molecular weight carbohydrate oligomer fractions.

Tannin and lignin were blended with polypropylene (PP) through dynamic vulcanization technique. Their influence of mechanical property, crystallinity, thermal stability, as well as ultraviolet (UV) protection property on the PP matrix was investigated and compared with native tannin and lignin. According to our experimental results, tannin and lignin undergo dynamic vulcanization and were more compatible with the PP matrix. Besides, tannin and vulcanized tannin can perform as nucleating agents of PP because of their relatively small particle size. Moreover, vulcanized tannin/lignin have a better performance on the thermal stability of PP compared with native tannin/lignin, especially PP/vulcanized lignin blend. Furthermore, vulcanized tannin/lignin present better UV protective performance, concluded from fewer changes on surface morphology, carbonyl index, crystallinity, viscosity, and tensile property.

To find the effects of cross-linker phenol-formaldehyde (PF) resin on the performance of soy-based adhesives, the reaction between model compounds hydroxymethyl phenol (HPF) and glutamic acid were studied in this paper. HPF prepared in laboratory conditions showed higher content of hydroxymethyl groups than normal PF resin, which was proved by the results of Electrospray Ionization Mass Spectrometry (ESI-MS) and 13C Nuclear Magnetic Resonance (13C-NMR). The results of ESI-MS, Fourier transform infrared spectroscopy (FT-IR), and 13C-NMR based on resultant products obtained from model compounds showed better water resistance of the soy protein-based adhesive modified by PF-based resin, which indicated the reaction between PF resin and soy protein. However, it seemed that the soy-based adhesive cross-linked by HPF with the maximum content of hydroxymethyl groups did not show the best water resistance.

The reaction of citric acid with wood veneers was studied by Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CP MAS 13C NMR) and matrix assisted laser desorption ionization time of flight (MALDI ToF) mass spectrometry. The analysis showed that reactions of citric acid occurred with both lignin and carbohydrate constituents of wood. The reactions occurring are esterifications between the carboxylic acid functions of citric acid and the numerous aromatic and aliphatic hydroxyl groups of the main wood constituents. Reaction of citric acid with glucose as a simple model compound of carbohydrates hydroxyl groups also yielded reactions leading to linear and branched oligomers by esterification. The result indicate that the reactions of esterification are accompanied in parallel by some internal rearrangements of lignin. The applied results on bonding wide flat wood surfaces such as veneers to obtain LVL panels yielded excellent strength results even if the conditions of pressing were more drastic than what is usual for this application. The applied bonding results have shown that citric acid has great potential to be used as a bio-binder for wood veneers.

Mostly biosourced non-isocyanate polyurethanes (NIPU) were prepared from mono- and disaccharides, namely glucose and sucrose, reacted with dimethyl carbonate and hexamethylene diamine. The main aim of this research was to show that NIPU can be prepared from mono- and disaccharides, this just being an initial exploratory work and its sole main aim. The oligomers obtained were detected by MALDI-ToF, CP-MAS 13C NMR, and FTIR spectrometries. The glucose-derived NIPU were shown to harden at a markedly lower temperature than the sucrose-derived ones and to be easier to handle and spread. The NIPU obtained were applied as wood and steel surface coatings and tested by the sessile drop test (on wood) and cross-cut test (on steel) with encouraging results. The glucose NIPU gave good surface coating results already at 103 °C, while the sucrose NIPU yielded good results only at a markedly higher temperature of hardening. The NIPU saccharide resins were also tested as thermosetting wood joint adhesives with the glucose NIPU yielding very encouraging results.

(MGG’) resin adhesives for bonding wood panels were prepared by a single step procedure, namely reacting melamine with glyoxal and simultaneously with a much smaller proportion of glutaraldehyde. No formaldehyde was used. The inherent slow hardening of this resin was overcome by the addition of N-methyl-2-pyrrolidone hydrogen sulphate ionic liquid as the adhesive hardener in the glue mix. The plywood strength results obtained were comparable with those obtained with melamine–formaldehyde resins pressed under the same conditions. Matrix assisted laser desorption ionisation time of flight (MALDI ToF) and Fourier transform Infrared (FTIR) analysis allowed the identification of the main oligomer species obtained and of the different types of linkages formed, as well as to indicate the multifaceted role of the ionic liquid. These resins are proposed as a suitable substitute for equivalent formaldehyde-based resins.

To guide the preparation of protein-based adhesive, especially the soy-based adhesive, the reaction between a simple dipeptide N-(2)-l-alanyl-l-glutamine (AG), being used as a model compound of protein, and its cross-linker furfuryl alcohol were studied in this paper. The products that were prepared with furfuryl alcohol and AG under different pHs were analyzed by ESI-MS, 13C NMR, and FT-IR. It was found that the medium environment had great effects on the competition of the co-condensation reaction between furfuryl alcohol and AG and self-condensation reaction of furfuryl alcohol molecules in the mixing system with furfuryl alcohol and AG. Under alkaline conditions, both co- and self-condensation were not obviously detected. Only when the value of pH was higher than 11, were a few co-condensation reaction products gotten. The reaction occurred mainly between furfuryl alcohol and the primary amido groups of AG. Under acid conditions, both co- and self-condensation were observed. The more acid the preparation conditions were, the easier to be observed the self-condensation of furfuryl alcohol molecules would be than the co-condensation between furfuryl alcohol and AG. When the value of pH was higher than 5, both co- and self-condensation were not outstanding. In this study, under pH 3, the co- and self-condensation found equilibrium. There was a great possibility for the primary amido and aliphatic amino groups of AG molecules to react with furfuryl alcohol molecules. No reaction was detected between the secondary amido groups of AG and furfuryl alcohol.

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.

Using non-toxic, low-volatile glyoxal to completely replace formaldehyde for preparing urea-glyoxal (UG) resin adhesive is a hot research topic that could be of great interest for the wood industry. However, urea-glyoxal (UG) resins prepared by just using glyoxal instead of formaldehyde usually yields a lower degree of polymerization. This results in a poorer bonding performance and water resistance of UG resins. A good solution is to pre-react urea to preform polyurea molecules presenting already a certain degree of polymerization, and then to condense these with glyoxal to obtain a novel UG resin. Therefore, in this present work, the urea was reacted with hexamethylene diamine to form a polyurea named HU, and then this was used to react it with different amounts of glyoxal to synthesize hexamethylenediamine-urea-glyoxal (HUG) polycondensation resins, and to use this for bonding plywood. The results show that the glyoxal can well react with HU polyuria via addition and schiff base reaction, and also the HUG resin exhibits excellent bonding strength and water resistance. The shear strength of the plywood bonded with this HUG at 160°C hot press temperature as high as 1.93 MPa, 2.16 MPa and 1.61 MPa, respectively, which meets the requirement of the China national standard GB/T 9846-2015 (≥0.7 MPa), and can be a good choice as a wood adhesive for industrial application. [ABSTRACT FROM AUTHOR]

This article presents the first applied results of using citric acid in combinations with a melamine-urea-formaldehyde (MUF) resin for bonding wood veneers. The chemical reactions involved are shown based on a MALDI ToF analysis of the reaction of the MUF resin with citric acid. The preliminary results of the physical and mechanical properties of the LVL prepared are also presented. Veneers from Populus sp were used to manufacture 5-layer laminated veneer lumber (LVL) of small dimensions. Five combinations of the amount of citric acid, MUF spread rate and pressing parameters were tested. LVL bonded with 20% of citric acid + 100 g/m² of MUF, hotpressed using a 3-step process with maximum 1.5 MPa of pressure yielded the board with better dimensional stability and mechanical properties. It could be concluded that citric acid in combination with MUF can be used for bonding wood veneer and the research should be continued to study further the parameters involved and to enhance the results. [ABSTRACT FROM AUTHOR]