The effect of the heat treatment of spruce wood on the curing of melamine–urea–formaldehyde and polyurethane adhesives

The effect of the heat treatment of spruce wood on the curing of melamine–urea–formaldehyde (MUF) and polyurethane (PUR) adhesives was monitored by measuring their rheological properties by means of a rheometer. Instead of the standard aluminium discs, wooden discs, made from heat-treated wood with different degrees of thermal modification and conditioned in different climates, were used. The wooden discs provided more realistic curing of the adhesives compared to the real-life bonding of wood, because of solvent absorption. The results of the rheological measurements suggested that the modified wood inhibited the curing of MUF and PUR adhesives. The curing of the MUF adhesive was slower because of the reduced absorption of water from the adhesive. The curing of the one-component PUR adhesive was affected by the lower moisture content (MC) of the modified wood.     

Evaluation of wood bonding performance of water-washed cottonseed meal-based adhesives with high solid contents and low press temperatures

Water-washed cottonseed meal (WCSM) has been shown as a promising bio-based wood adhesive. In this work, we tested the bonding strength of WCSM slurries with high solid contents and low press temperatures per industrial input for non-structural applications as European Standard Class D1 wood adhesives. Increasing the WCSM content from 11 to 20% and 30% did not substantially change the adhesive strength but increased the viscosity of WCSM slurries dramatically. The shear strength at break of the maple wood pairs bonded at 40 and 60 °C was lower than that of maple pairs bonded at 100 °C. However, the shear strength of the pairs bonded at lower temperatures (40 and 60 °C) could be improved by extending the press time from 20 to 120 min. Addition of citric acid (CA) improved the viscosity of the WCSM adhesive at 20% solid content, but lowered the adhesive strength. The addition of denaturing reagent sodium dodecyl sulfate (SDS) showed reverse impacts on the adhesive strength and viscosity, compared to CA addition. Based on these observations, eight adhesive slurries were formulated with 20 and 30% of WCSM, 3% of CA or SDS, or 9.6% or 19.1% of denaturing reagent guanidine hydrochloride (GdmCl), and their bonding strengths were tested. These formulations could be used as the basis for developing low temperature WCSM-based wood adhesives to meet the criteria of both operational flowability and shear strength of the domestic furniture and small utensils niche markets for forest products.     

Effect of pressing parameters on the shear strength of beech specimens bonded with low solvent liquefied wood

Liquefied wood (LW) is a naturally based product which has the potential to be used as an adhesive. It can be used as a part of a polymer formulation, as a part of an adhesive mixture with commercial adhesives, or as an independent material for wood bonding. In this study, wood was liquefied at 180?°C using ethylene glycol as the solvent and sulphuric acid as a catalyst. In the first part of research, LW with different pH values was used for the bonding of solid wood at 200?°C for 15?min. In the second part, LW with an optimal pH value was used for bonding at different press temperatures for 15?min. In the third part, the minimum pressing time at the optimal pH value and at the optimal press temperature was determined. Unmodified LW with a negative pH value, a press temperature of 180?°C, and a pressing time of 12?min was determined to be optimal (based on highest shear strength) for the bonding of 5?mm thick wood lamellas with the LW used in this study. At these conditions bonds exhibited shear strength of around 7?N/mm² which was too low to attain standard requirements. Despite this, high wood failure (100%) was observed as a consequence of low pH value and high press temperature which caused damage of the part of beech lamellas where LW was applied.     

A Soy Flour-Based Adhesive Reinforced by Low Addition of MUF Resin

The desire to prepare a lower-cost soy-based adhesive has led to an interest in using the abundant and inexpensive soy flour (SF) as a substitute for expensive soy protein isolates (SPI) in wood adhesives. However, the weakness of this adhesive is poor water-resistance and bonding strength due to a low protein content, which limits its application in the wood industry. The objective of this research was to provide a simple and useful approach for improving the adhesion performance of SF-based adhesive by introducing a small addition of melamine-urea-formaldehyde (MUF) resin into the cured system. The optimum addition level of MUF resin, as well as the adhesion performance and conformation change of SF-based adhesive, were investigated. The analytical results indicated that the co-condensed methylene bridges were formed through the reaction of methylol groups of MUF resin with soy units during the hot-press process. The addition of MUF resin, not only significantly decrease the viscosity of SF-based adhesive but also increase its water-resistance and wet shear strength value. The SF-based adhesive containing 20% MUF resin, is a relatively low-cost adhesive, has a reasonable viscosity, and moreover can pass the Chinese Industrial Standard requirement (0.7 MPa) for interior plywood panels.     

Adhesive characteristics and bonding performance of phenol formaldehyde modified with phenol-rich fraction of crude bio-oil

Commercial phenol–formaldehyde (PF) adhesive was gradually substituted by increasing amount of the phenol-rich fraction (PRF) of crude bio-oil up to 40 wt%. The effect of substitution level of the PRF on the chemical, curing, morphological scanning electronic microscope (SEM), and bonding characteristics of the PF adhesive was determined. The tensile-shear strength of single lap-joint wood specimens bonded with the modified PF adhesives was investigated under indoor and outdoor exposure conditions. The chemical composition of the PRF was investigated using some chromatographic and spectroscopic techniques. Further structural analysis of PRF-modified PF adhesives was determined using Fourier transform infrared spectroscopy (FTIR). The PRF resol had a similar molecular structure to commercial pure phenol resol adhesive. The PRF could be partially substitute for the petroleum-based phenol in commercial PF adhesives with inexpensive phenols derived from lignocellulosic wastes.     

Adhesive properties of water-washed cottonseed meal on four types of wood

The interest in natural product-based wood adhesives has been steadily increasing due to the environmental and sustainable concerns of petroleum-based adhesives. In this work, we reported our research on the utilization of water-washed cottonseed meal (WCM) as wood adhesives. The adhesive strength and water resistance of WCM adhesive preparations on poplar, Douglas fir, walnut, and white oak wood veneers were tested with press temperatures of 80, 100, and 130 °C. Our data indicated that raising the hot press temperature from 80 to 100–130 °C greatly increased the bonding strength and water resistance of the WCM adhesives. The general trend of the adhesive strength of WCM on the four wood species was Douglas fir > poplar ≈ white oak > walnut. The rough surface of Douglas fir with tipping features could enhance the mechanical interlocking between the wood fibers and adhesive slurry, contributing to the high adhesive strength. The dimensional swelling of the bonded wood pairs due to water soaking was in the order: thickness > width (i.e. perpendicular to the wood grain) > length (i.e. parallel to the wood grain). The greatest dimensional changes were observed in Douglas fir specimens. However, the highest decrease in adhesive strength by water soaking was with poplar wood specimens. These observations suggested that the wood dimensional changes were not dominant factors on water weakening the bonding strength of these wood pairs.     

Investigation of formaldehyde-free wood adhesives from kraft lignin and a polyaminoamide–epichlorohydrin resin

A formaldehyde-free wood adhesive system consisting of kraft lignin and a polyaminoamide-epichlorohydrin (PAE) resin (a paper wet strength agent) has been investigated in detail. The lignin-PAE adhesives were prepared by mixing an alkaline kraft lignin solution and a PAE solution. Mixing times longer than 20 min had little impact on the shear strength of the wood composites bonded with the lignin-PAE adhesives. The shear strength of the wood composites bonded with the lignin-PAE adhesives increased and then flattened out when the press time and the press temperature increased. The shear strength and water resistance of the wood composites bonded with the lignin-PAE adhesives depended strongly on the lignin/PAE weight ratio. Of the weight ratios studied, the 3:1 lignin/PAE weight ratio resulted in the highest shear strength and the highest water resistance of the resulting wood composites. The wood composites bonded with the lignin-PAE adhesives did not delaminate and retained very high strengths even after they underwent a boiling-water test. The lignin-PAE adhesives could be stored at room temperature for two days without losing their adhesion ability. PAE was the crosslinking agent in this lignin-PAE adhesive. Possible reactions between lignin and PAE are discussed in detail.     

Impact of curing condition on pH and alkalinity/acidity of structural wood adhesives

Nine formulations were selected for evaluating the effect of different curing methods on pH and alkalinity or acidity of various structural wood adhesives. These included four phenol–formaldehyde (PF) resins with high pH, one phenol–resorcinol–formaldehyde (PRF) resin with intermediate pH, two melamine–urea–formaldehyde (MUF) resins, and two melamine–formaldehyde (MF) resins with low pH. The four curing methods used in the study were: (1) curing at 102–105°C for 1 h (based on CSA O112.6‐1977), (2) four‐hour curing at 66°C followed by 1‐hour curing at 150°C (based on ASTM D1583‐01), (3) curing at room temperature overnight (based on ASTM D 1583‐01), and (4) cured adhesive squeezed out from glue lines of bonded shear block samples. The effect of the different methods on pH and alkalinity/acidity of the cured adhesive depended strongly on the individual adhesives. For the PF, the alkalinity was different for the different formulations in the liquid form, while in the cured form, the difference in the alkalinity depended on the curing method used. The MF and the MUF were the adhesives most affected by the method used. In particular, the MUF showed much higher cured film pH values when cured by method 2 compared to the other three methods, while both the cured MF and MUF exhibited quite variable acidity values when cured with the different methods. The PRF showed reasonably uniform cured film pH but varying acidity values when cured with the different methods. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Wood processing variables and adhesive joint performance

In order to obtain a bonded wood product from the tree, wood must be subjected to a series of processes. These include, among others, vital processes like drying of the green wood and machining of the surfaces of the dried wood in preparation for bonding. However, when wood is machined with dull blades, thermal degradation of the wood frequently occurs. The effects of kiln drying and thermal degradation of wood on the performance of the adhesive joints subsequently formed from such wood were investigated. Tapered double cantilever beam (TDCB) test specimens obtained from hard maple and phenol–resorcinol–formaldehyde (PRF) adhesives were used in the investigations. The enhancement of fracture energy due to the reduction in the moisture content of wood, the improved performance of adhesive joints due to rejointing of wood surfaces before bonding, and the reduction of adhesive joint strength resulting from thermal degradation of wood are presented and discussed.     

Rubber solution adhesives for wood-to-wood bonding

Rubber solutions were prepared and used for bonding wood pieces. The effect of the variation of chlorinated natural rubber (CNR) and phenolformaldehyde (PF) resin in the adhesive solutions on lap shear strength was determined. Natural rubber and neoprene-based adhesive solutions were compared for their lap shear strength. The storage stability of the adhesive prepared was determined. The change in lap shear strength before and after being placed in cold water, hot water, acid, and alkali was tested. The bonding character of these adhesives was compared with different commercially available solution adhesives. The room-temperature aging resistance of wood joints was also determined. In all the studies, the adhesive prepared in the laboratory was found to be superior compared to the commercial adhesives. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1185–1189, 1998     

Adhesive and curing properties of chicken feather/blood-based adhesives for the fabrication of medium-density fiberboards

This study was conducted to investigate the adhesive properties of chicken feather (CF)-based adhesives for wood-based panels. CF was hydrolysed in sodium hydroxide solutions of 5%, 7.5% and 10% (CF-AK). Chicken blood (CB) hydrolysed in sulfuric acid solution of 5% (CB-AC) was used as a hardener. The adhesives were formulated by crosslinking 60% CF-AK, 10% CB-AC and 30% formaldehyde-based crosslinking agents (formalin, melamine-urea-formaldehyde and phenol-formaldehyde prepolymers) on a solid weight basis. The CF-based adhesives were very viscous at room temperature, but the viscosity at 50 °C ranged from 300 to 600 mPa·s resulting in a sprayable adhesive. From the DSC analysis, the use of CF-AK-10% in the CF-based adhesives need longer curing time compared with that of CF-AK-5%. Most mechanical strength properties and dimensional stability of MDF bonded with CF-based adhesives were similar to those of commercial urea-formaldehyde (UF) resin. However, internal bonding strength of most MDF bonded with CF-based adhesives was higher than that with the UF resin. Most adhesive properties of the MDF manufactured with the new CF adhesive met the Korean Standard requirements for interior MDF. These results suggest that CF and/or CB can be used as raw materials for environment-friendly adhesives for producing wood panels.     

Morphologic accessibility of wood adhesives

Accessibility of wood adhesives was determined using a potassium bromide-embedding technique during resin cure. Cured resin was then extracted with water, followed by x-ray analysis of residual potassium bromide retention in the adhesive matrix. Cured urea–formaldehyde (UF), phenol–formaldehyde resol (PF), and phenol–resorcinol formaldehyde (PRF) accommodated large quantities of potassium bromide. However, only PRF adhesive showed crystallization of trapped potassium bromide, suggesting the presence of large pore sizes in the polymer lattices. Both UF and PRF adhesives, after room-temperature soaking, were equally resistant to water access. At higher temperature, water accessibility of UF increased greatly which may be attributed to thermal softening of the adhesive, while the accessibility of water to the PRF adhesive matrix was mainly a surface phenomenon and was not very temperature dependent. PF was highly accessible to water, even at room temperature, as a result of swelling from the presence of sodium hydroxide (catalyst). Accessibility of PRF adhesive was greatly increased by base (NaOH) solutions but not by acid (H₂SO₄) solutions. The UF resin showed slight increase of accessibility with increase in acidity and basicity of the water solution, but the accessibility increase of this adhesive in base solution was substantially less than that of PRF. The acid hydrolysis influence on accessibility increase of UF adhesive was far less severe than that of temperature.     

Effects of boron compounds on the bonding strength of phenol-formaldehyde and melamine-formaldehyde adhesives to impregnated wood materials

Wood materials are increasingly being used in the construction of structural beams, sports equipment, etc. This study was carried out to determine the bonding strength of phenol-formaldehyde (PF) and melamine-formaldehyde (MF) adhesives to impregnated wood materials. For this purpose, brutia pine (Pinus brutia Ten) and elm (Ulmus compestris L.) woods were impregnated with borax (Bx), boric acid (Ba), Bx + Ba (wt:wt 50:50%), di-ammonium phosphate (D), [D + (Bx + Ba)]/(50 + (25 + 25%), w/w) and Tanalith-C 3310 (T-C 3310) using the vacuum method according to ASTM-D 1413-76. The effects of wood species, impregnating material and type of adhesive on the bonding strength were determined. The highest shear strength (11.09 N/mm²) was obtained from elm wood control (i.e., without any impregnating materials) samples with MF; thus, the impregnation process negatively affected the adhesive bonding strength. Impregnating materials, especially those containing oily or similar solutions such as T-C 3310, are not advised for wood elements which are subjected to shear.     

三聚氰胺添加方式对MUF胶粘剂性能的影响

以三聚氰胺作为脲醛树脂(UF)的共聚改性剂制备MUF(三聚氰胺甲醛树脂)胶粘剂。探讨了三聚氰胺的添加方式对MUF胶粘剂性能的影响,同时对其固化特性、分子结构和耐热性等进行了分析。结果表明:三聚氰胺2次投料法可有效降低MUF胶粘剂的甲醛释放量,但其胶接强度也随之下降;同时,该MUF固化体系的外推固化温度、表观活化能和反应级数均有所增加,耐热性降低;另外,2次投料体系使MUF的相对分子质量降低、相对分子质量分布变宽。     

Influence of humidity and frequency on the energy dissipation in wood adhesives

In this paper, the frequency dependent energy dissipation of typical wood adhesive under cyclic stress was studied on film adhesive samples. Three moisture-curing one component polyurethane (1C-PUR) adhesives with relative ductile behavior, one melamine formaldehyde (MF) and one phenol formaldehyde resorcinol (PRF) adhesives both with a more brittle behavior were prepared to study the viscoelastic properties at different relative air humidities (RH). Dynamic Mechanical Analysis (DMA) in tensile mode was used to determine loss modulus, storage modulus and loss factor Tan Delta on free standing adhesive films. It has been shown that 1C-PUR adhesives dissipate proportional more of the stored energy than MF and PRF adhesives. Humidity increased the dissipative processes in all PUR adhesives, especially in the polyamide fiber filled adhesive. PRF adhesive is less influenced by humidity. While for all other tested adhesives the dissipative processes generally increased with higher humidity, humidity decreased the damping of the investigated MF adhesive. The influence of the frequency on the energy dissipation is low for all tested adhesives in the investigated frequency range. Further fatigue tests with glued wood samples are needed to confirm the results observed on the free standing adhesive films.     

木材用聚氨酯胶黏剂的研究进展

聚氨酯胶黏剂由于具有无甲醛,施胶量少,胶接强度高等众多优点,使其在木材工业中的使用量逐步增加.但由于价格因素,聚氨酯胶黏剂在木材用胶黏剂中所占的比例仍然较小.研究聚氨酯胶黏剂与木材的胶接机理是从原理入手,掌握聚氨酯胶黏剂的胶接特点,用最少的原料来达到最好的胶接效果,以希望降低使用价格,扩大应用范围.简述聚氨酯胶黏剂的优点,开发和改性研究的基本思路,重点综述了国内外聚氨酯胶黏剂与木材胶接机理的研究进展.     

Adhesives formulated with chemically modified okara and phenol–resorcinol–formaldehyde for bonding fancy veneer onto high-density fiberboard

With an abrupt increase of petrochemical prices and the critical environmental issue related to the volatile organic compounds emitted from the adhesive resins, the development of environmentally friendly new adhesive systems is common issue. In our study, the okara, which is a residue from the production of tofu, was introduced to develop competitive bio-based adhesives for the production of fancy-veneered floor boards. Okara (AC and AK) was hydrolyzed with 1% sulfuric acid solution and 1% sodium hydroxide solution. Phenol–resorcinol–formaldehyde (PRF) prepolymer was prepared as a crosslinker of AC and AK. Adhesive resins were formulated with AC, AK and PRF prepolymer. The adhesive resins were used to fabricate floor boards composed of oak veneers onto high-density fiberboard. The experimental variables were three weight ratio of AC/AK to PRF (45/45/10, 40/40/20 and 35/35/30), three assembly time (0, 10 and 20 min), and two press time (90 and 120 s), respectively. The fancy-veneered high-density fiberboards were prepared and subject to testing of the dry tensile strength, glueline failure by wetting and formaldehyde emission. Dry tensile strengths of the boards exceeded the requirement of KS standard. The formaldehyde emissions were satisfied with the limitation specified in KS standard. Based on these results, okara has a potential to be used as a renewable raw material of environmentally friendly adhesive resin systems for production of floor boards, but further researches, such as biological hydrolysis of okara and various formulations of PRF prepolymer, are required to improve the adhesive strength and to reduce formaldehyde emission of okara-based adhesive resins.     

Improving performance of polyvinyl acetate (PVA) as a binder for wood by combination with melamine based adhesives

In this study blending PVA with MUF and MF was evaluated as an approach to enhance the performance of PVA towards water and elevated temperatures. MF and MUF were added to PVA at different proportions: 15%, 30%, 50%, 70% and 100%. Blends of PVA with MF and MUF were used as adhesives to bond wood joints. The shear strength of wood joints was measured at dry and wet states, and elevated temperatures. Thermogravimetric analysis was used to study thermal stability of PVA and its blends with MF and MUF. The structural changes caused by the inclusions were characterized by Fourier transforms infrared spectroscopy (FT-IR). The results showed that shear strength of wood joints were improved by the addition of MF and MUF to PVA in all conditions. Adding small amounts of MUF or MF (as low as 15%) enhanced the performance of wood joints towards water and elevated temperatures. The extent of improvement was sometimes so high that the strength of glue line surpassed strength of wood in wet conditions leading to wood failure rather than glue failure. MF had more effectiveness in improving shear strength of wood joints than MUF in all conditions. Thermal stability of PVA was increased by MF but the effect of MUF on thermal stability of PVA was dependent on MUF proportions and temperatures. FT-IR analyses showed that there are some chemical bonds between PVA and MF. Considering costs, effectiveness and formaldehyde emission, adding 15% MF to PVA seems the optimal proportion of MF in the PVA blends.     

Evaluation of adhesion properties of blends of cottonseed protein and anionic water-soluble polymers

There is increasing interest in agro-based, biodegradable and eco-friendly wood adhesives as partial replacements for petroleum-based adhesives. In this work, we studied the adhesion of cottonseed protein isolate (CPI) blended with several anionic water-soluble polymers. Anionic vinyl polymers studied included poly(acrylate), poly(acrylate-co-acrylamide), poly(vinyl sulfate), poly(vinyl sulfonate), and poly(vinyl phosphonate). Anionic polysaccharides studied included three types of carrageenan, carboxymethyl cellulose (CMC), low-methoxy pectin, alginate, and chondroitin sulfate. In general, the adhesive strength of CPI increased with the addition of anionic polymer up to a certain level and then decreased with further polymer addition. Different anionic polymers showed different enhancements. The best result for vinyl polymers was observed for the CPI/poly(vinyl sulfate) blend, which exhibited a 30% improved dry strength over CPI alone. The best results for the polysaccharides were obtained for the CPI/CMC and CPI/pectin blends, with improvements in dry adhesive strength over the CPI control of 66% and 50%, respectively. The CPI/CMC and CPI/pectin blends also showed improved hot water resistance. These findings suggest that the CPI/anionic polymer blends might be useful components in biobased wood adhesive formulations.     

Plant Polyphenol-Inspired Crosslinking Strategy toward High Bonding Strength and Mildew Resistance for Soy Protein Adhesives

Soybean protein adhesives are environmentally friendly biomass-based aldehyde-free adhesives that have good economic value for the wood industry; however, it remains challenging to produce soybean protein adhesives with excellent water resistance, toughness, and mildew resistance through a simple modification method. In this work, inspired by plant polyphenols, a novel crosslinked soybean meal adhesive (SMPT) is obtained using a facile economic method. Polyamidoamine-epichlorohydrin (PAE) and tannic acid (TA) are combined with a soybean meal matrix to form a tough co-crosslinked network through strong intermolecular forces (covalent bonds, ionic bonds, and hydrogen bonds) in adhesive system. The results show that the wet bonding strength of SMPT adhesives for plywood is 134.1% higher than the unmodified soybean meal adhesive. The adhesion properties met the standard requirements for interior-use plywood. And the compact cross-linking network structure is accelerated the greater energy dissipation, which improves the toughness of adhesive. Moreover, cationic azetidinium groups in PAE and phenol hydroxyl groups in TA synergistically not only exhibit the good antibacterial activities but also improve mildew resistance for SMPT adhesives. This facile strategy provides an economic sustainable method to prepare high-performance environmentally friendly wood adhesives.