Composites using agricultural and forestry residues as raw materials with potentially high-performance, multifunctional and biodegradable ecological advantages, are viewed as very promising for new-generation lightweight and low-cost bio-based sustainable building materials. At present, the research on wood-plastic composite materials is relatively mature. However, it is still a challenge to effectively use other biomass and improve the interface of the high-polymer compound system. Herein, we proposed a simple and effective method to enhance the interfacial adhesion properties of rice husk fibre and High Density Polyethylene (HDPE) composites by the silane coupling agent KH-550 and compatibilizer Maleic anhydride grafted polyethylene (MAPE) with complementary modification. It was found that the coupling agent KH-550 cross-linked with the hydroxyl group on the husk fibre surface and solidified with the high polymer by –NH–, –C=O– functional group generation. Compatibilizer MAPE strengthened the two phases by covalently bonding with an ester linkage and lowered the roughness of the cross-section of the composites. Meanwhile the modification enhanced the dispersibility, and mechanical properties of the husk-high polymer compound system, the bending and flexural strength were improved by 11.5% and 28.9% with KH-550, and MAPE added, respectively. The flexural strength of the composites increased by 40.7% after complementary modification. Furthermore, the complementary modification treatment reduced the hydrophilic hydroxyl groups and increased the molecular chain to improve the water-resistance, elastic modulus and toughness of the composite. This study prepared a bio-composite, which is expected to expand the use of agricultural and forestry residues as an extension of wood-plastic composites.
The use of cost effective solvents may be necessary to store wood pyrolysis bio-oil in order to stabilize and control its viscosity, but this part of the production system has not been explored. Conversely, any rise in viscosity during storage, that would occur without a solvent, will add variance to the production system and render it cost ineffective. The purpose of this study was to modify bio-oil with a common solvent and then react the bio-oil with an epoxy for bonding of wood without any loss in properties. The acetone pretreatment of the bio-oil/epoxy mixture was found to improve the cross-linking potential and substitution rate based on its mechanical, chemical, and thermal properties. Specifically, the bio-oil was blended with epoxy resin at weight ratios ranging from 2:1 to 1:5 and were then cured. A higher bio-oil substitution rate was found to lower the shear bond strength of the bio-oil/epoxy resins. However, when an acetone pretreatment was used, it was possible to replace the bio-oil by as much as 50% while satisfying usage requirements. Extraction of the bio-oil/epoxy mixture with four different solvents demonstrated an improvement in cross-linking after acetone pretreatment. ATR-FTIR analysis confirmed that the polymer achieved a higher cross-linked structure. DSC and TGA curves showed improved thermal stability with the addition of the acetone pretreatment. UV-Vis characterization showed that some functional groups of the bio-oil to epoxy system were unreacted. Finally, when the resin mixture was utilized to bond wood, the acetone pretreatment coupled with precise tuning of the bio-oil:epoxy ratio was an effective method to control cross-linking while ensuring acceptable bond strength.
As a byproduct from the soybean oil industry, soy meal can be reproduced into value-added products to replace formaldehyde as a plywood adhesive. However, the use of soy meal has been limited by its poor antifungal and antiseptic properties. In this work, three kinds of material, namely nano-Ag/TiO2, zinc pyrithione, and 4-cumylphenol were applied to enhance the mildew resistance of soy meal via breakdown of the cellular structure of mildew. The fungi and mold resistance, morphology, thermal properties, and mechanism of the modified soy meal were evaluated. The success of the antifungal and antiseptic properties was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy. The results indicated that all three kinds of material improved the fungi and mold resistance of soy meal, and sample B, which was modified with a compound of nano-Ag/TiO2 and zinc pyrithione, was the effective antifungal raw material for the soy-based adhesives. FTIR indicated that the great improvement of antifungal properties of soy meal modified with 4-cumylphenol might be caused by the reaction between COO– groups of soy protein. This research can help understand the effects of the chemical modification of nano-Ag/TiO2, zinc pyrithione, and 4-cumylphenol on soy meal, and the modified soy meal exhibits potential for utilization in the plywood adhesive industry.
Bio-based adhesives have low water resistance and they are less durable than synthetic adhesives, which limits their exterior applications. In this study, a bio adhesive was developed from soybean meal and larch tannin that was designed for exterior use. Phenol hydroxymethylated tannin oligomer (PHTO) was synthesized and then mixed with soybean meal flour in order to obtain a soybean meal-based adhesive (SPA). The results showed that the moisture absorption rate, residual rate, and solid content of SPA with 10 wt % PHTO (mass ratio with respect to the entire adhesive) were improved by 22.8%, 11.6%, and 6.8%, respectively, as compared with that of pure SPA. The wet shear strength of plywood with SPA with 10 wt % PHTO (boiling in 100 °C water for 3 h) was 1.04 MPa when compared with 0 MPa of pure SPA. This met the bond strength requirement of exterior-use plywood (GB/T 9846.3-2004). This improved adhesive performance was mainly due to the formation of a crosslinked structure between the PHTO and the protein and also PHTO self-crosslinking. The formaldehyde emission of the resulting plywood was the same as that of solid wood. The PHTO-modified SPA can potentially extend the applications of SPAs from interior to exterior plywood.