Evaluation of block shear properties of selected extreme‐pH structural adhesives by short‐term exposure test

Nine structural adhesives with varying pH were selected to examine the effect of adhesive pH on wood–adhesive bond quality. The adhesives evaluated included four highly alkaline phenol–formaldehyde, one intermediate pH phenol–resorcinol–formaldehyde, two acidic melamine–urea–formaldehyde, and two acidic melamine–formaldehyde resins. Block shear specimens were prepared using Douglas‐fir and black spruce wood. The adhesive performance was evaluated by measuring the shear properties (strength and wood failure) of the specimens tested at the dry and vacuum–pressure–redry (VPD) conditions. Adhesive pH, test condition, and wood species showed significant effects on shear properties. The different adhesives performed differently at the dry and VPD conditions. The high‐pH adhesives (phenol–formaldehyde and phenol–resorcinol–formaldehyde) showed similar high wood failures at both test conditions and performed better than the low‐pH adhesives (melamine–formaldehyde and melamine–urea–formaldehyde), especially after the VPD conditioning. The low‐pH adhesives showed high wood failure at the dry condition, but wood failure decreased significantly after VPD conditioning for both species, indicating that the low‐pH adhesives were less durable than the high‐pH adhesives. High‐pH adhesives did not have a negative impact on the strength of the bonded specimens. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Wood Adhesives Based on Alkaline Extracts from Wastewater Biosolids and Mustard Protein

This work reports on the dry adhesion strength of wood adhesives formulated with fractions of an alkaline extract obtained from wastewater activated sludge, a renewable and abundant resource. The extract was fractionated and desalted using ultrafiltration techniques. The effect of molecular weight and composition (protein and carbohydrate content) on the extract’s adhesion strength was assessed, as well as the effect of crosslinking using glutaraldehyde. The dry adhesion strength of adhesives formulated with soluble mustard seed protein isolate, a protein-rich alkaline extract, is also reported. In the presence of glutaraldehyde, an extract fraction with high protein content and low salt and hydroxide content showed adhesion strength close to that of the mustard protein adhesive and a commercial wood adhesive. It was further determined that the adhesion strength of the extract and its fractions was strongly correlated with their protein content.     

Effect of a coupling agent on the adhesion of paint to timber

A method of treating timber before applying a coating has been developed and tested. An organofunctional silane coupling compound was found that was capable of reacting and forming bonds with both wood and a range of coatings. Wet and dry adhesion strength between a range of coatings and wood has been determined by the direct pull-off test under a variety of test conditions. The data presented show how the bridging of the interface between wood and coating can, with some coatings, improve not only the initial bond strength but also provide significantly higher wet adhesion strength and long-term bond durability.     

An eco-friendly and high shear strength adhesive from catechol-modified polyethyleneimine

Conventional adhesives often emit volatile organic compounds (VOCs), which have a negative impact on human health. In this paper, an environmentally-friendly supramolecular adhesive PD which has high adhesive and low VOCs emission is prepared by the reaction between polyethyleneimine (PEI) and 3,4-dihydroxybenzaldehyde (DBA). PD containing abundant catechol groups exhibit excellent adhesion to wood substrates and is able to reach a maximum shear strength of 5.20 ± 0.39 MPa. One factor is attributed to multiple reactions between PEI, and DBA and oxidation of DBA. These reactions construct a complex three-dimensional cross-linked structure which is very helpful to improve the bonding performance of the adhesive. Another reason refers to the fact that a large number of catechol groups in PD can form a lot of hydrogen bonds with the amino group in PEI and the hydroxyl group in the wood substrate. These hydrogen bonds play an important role in enhancing shear strength. PD adhesives have a stronger bond strength than commercial chloroprene rubber (CR, Pattex-PXL) and polyvinyl acetate adhesives (PVAc, JUJU-8708) and have lower emissions of VOCs. As an environmentally-friendly adhesive for wood-based substrates, this adhesive may have potential applications in the wood processing industry.     

淀粉基木材胶黏剂研究现状与展望

利用廉价的淀粉开发高性能的木材胶黏剂是人类永久的梦.但是传统的淀粉胶黏剂不能用于木材的黏结.早期的淀粉基木材胶黏剂研究是将淀粉在强烈的反应条件下转化为低分子物质来充当酚醛胶的填料.而目前的发展趋势是既要考虑充分利用淀粉的大分子特性,避免过度降解,又要能够向淀粉链中引入足够的均匀分布的化学键,使其与氢键的弱化学作用力有效配合,达到木材胶黏剂耐水的要求.双醛淀粉树脂胶;淀粉、聚乙烯醇和六甲氧甲基三聚氰胺共混胶;淀粉氧化降解接枝改性聚氨酯型胶等都是这类努力的代表性工作.我们的研究结果表明,淀粉经常压快速液化可以制备高活性的多羟基化合物.利用淀粉基多羟基化合物与多元酸（酐）聚合成功地制备了新型聚酯型的木材胶黏剂,成本与酚醛树脂相当,但其施胶量仅为酚醛树脂的1/3～1/2,可以用于高耐水性胶合板的生产.     

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.     

Biocompatible Catechol-Functionalized Cellulose-Based Adhesives with Strong Water Resistance

Numerous traditional adhesives have good adhesion in dry environments. However, non-environmental-friendliness and poor water resistance largely limit their practical applications. To prepare biocompatible adhesives with strong water resistance and adhesion strength, in this paper, catechol-functionalized cellulose-based adhesive polymers are synthesized by grafting N-(3,4-dihydroxyphenethyl)methacrylamide and methyl methacrylate onto cellulose chain through atom transfer radical polymerization (ATRP). The successful synthesis of the catechol-functionalized cellulose-based adhesive polymers is confirmed by FTIR and ¹H NMR. The different characteristics of the adhesive polymers, such as thermal stability, swelling ratio, biocompatibility, and adhesion strength are investigated. Strong water resistance on various substrates is realized in underwater environment for the catechol-functionalized cellulose-based adhesive with addition of Fe³⁺. The adhesion strength and thermal stability are enhanced when the catechol content is increased. The adhesive with catechol content of 25.4% shows the adhesion strength of 0.45 MPa for iron substrate in underwater environment. In addition, the adhesive with addition of Fe³⁺ exhibits excellent adhesion in dry environment, with maximum adhesion strength of 3.50 MPa for iron substrate. The cell culture test shows that the adhesive polymers have excellent biocompatibility. The biocompatible adhesives with strong water resistance have potential application in electronic, wood, and building fields.     

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.     

Preparation and characterization of wood polyalcohol‐based isocyanate adhesives

Sugi (Criptmeria Japonica) wood meal was liquefied at 150°C with a mixture of poly(ethylene glycol) 400 and glycerin in the presence of a sulfuric acid catalyst. The resulting liquefaction products were used directly to prepare isocyanate adhesives via mixing with polymeric diphenylmethane diisocyanate without the removal of the residue. The properties of the liquefaction products and the performances of bonded plywood were tested. The results showed that the residue content decreased and the hydroxyl value increased as the reaction time increased. The viscosity and weight‐average molecular weight significantly changed with the reaction time. All the dry test results of the shear strength met the Japanese Agricultural Standard (JAS) criteria for plywood. After a cyclic steaming treatment, however, only the plywood bonding with adhesives from the liquefied wood with a reaction time of 1.5 h satisfied the JAS criteria. The wood failure was very low. The emissions of formaldehyde and acetaldehyde were extremely low. Liquefied‐wood‐based isocyanate adhesives have the potential to become ideal wood adhesives because of their bond durability, safety, and recyclability.     

Mussel adhesive protein as an environmentally-friendly harmless wood furniture adhesive

Recent adhesive technologies have focused on the development of high-quality and eco-friendly adhesives. Thus, there is a gradual shift from the currently used chemical-based adhesives toward harmless adhesives with improved quality and performance. Here, we evaluated the potential use of bacteria-produced recombinant mussel adhesive protein (MAP) as a harmless wood furniture adhesive. We formulated a MAP wood adhesive as an inclusion body type for economical preparation, and we confirmed its harmlessness through the non-detection of volatile organic compounds and heavy metals. The formulated MAP showed sufficiently strong bulk adhesive strength for the dried gluing of wood adherends. We also found that the formulated MAP wood adhesive exhibits robust adhesion in various environmental conditions, including open assembly times, incubation times, temperatures, and humidity levels. In summary, the developed recombinant MAP could be successfully used as a promising environmentally-friendly, harmless wood furniture adhesive.     

Vapor Phase Acetylation of Southern Pine,Douglas-Fir,and Aspen Wood Flakes

Abstract

Southern pine, Douglas-fir, and aspen wood flakes were acetylated with acetic anhydride vapor and compared with flakes acetylated with liquid acetic anhydride diluted with xylene. The rate of acetylation was much lower for the vapor than for the liquid phase reaction. Acetylation weight percent gains above 20 were achieved by both methods. Flakeboards made from both types of flakes absorbed much less water, both in water soaking tests and when subjected to humid air, and swelled at a lower rate and to a lower extent than did control boards. At low weight gains of vapor phase acetylation, the rate and extent of swelling were higher than those found for the controls.

Hygroscopicity of the resulting flakeboards decreased with increased level of wood acetylation. The equilibrium moisture content for flakeboards made from liquid phase acetylated flakes was the lowest at each relative humidity tested as compared to control boards, and boards made from vapor acetylated flakes at the same weight gain.     

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.     

An innovative biomass-based wood adhesive generated from peony seed meal: Its preparation and properties

Plant protein-based adhesives, particularly those derived from soybean meal (SM), have been available for various product applications. However, the high cost of SM has limited large-scale manufacturing, despite sufficient production capacity. Peony seed meal (PSM) is abundant in proteins, polysaccharides, and polyphenols, the protein in PSM contains highly hydrophobic amino acids, resulting in low water solubility and water holding capacity. It is worth investigating whether the unique composition of hydrophobic amino acids in PSM protein can enhance the water resistance of PSM-based adhesives. Additionally, the lower price of PSM, which is approximately two-thirds of the cost of SM, makes it a more valuable raw material for adhesives. Herein, we report a simple and practical approach for preparing PSM-based wood adhesives by utilizing the highly active cross-linking agent of polyamidoamine-epichlorohydrin (PAE). The results showed PSM-based adhesives possessed excellent adhesion, especially the adhesive of “PSM-36%”, with the wet bond strength and the aged bond strength reaching 1.60 and 0.83 MPa, respectively, meeting the standards outlined for indoor-use plywood (≥0.98 MPa). Mechanistic studies indicated that the adhesion mechanism of such PSM-based adhesives might involve high solid content, low viscosity, high thermal stability, and the formulation of covalent bonds and hydrogen bond networks.     

Effects of adding nano-clay (montmorillonite) on performance of polyvinyl acetate (PVAc) and urea-formaldehyde (UF) adhesives in Carapa guianensis,a tropical species

The aim of this study was to improve the bond strength resistance of polyvinyl acetate (PVAc) and urea-formaldehyde (UF) adhesives modified with nano-clay (montmorillonite) with a tropical species of wood known to exhibit adhesion related problems. These adhesives were evaluated with 1.0 and 1.5 wt% nano-clay concentrations with lap shear strength (SS), and the percentage of wood failure (PWF) in dry and wet conditions being evaluated. An additional aim of this study was to observe the presence of nano-clay within both adhesive types using Atomic Force Microscopy (AFM) and the Transmission Electron Microscopy (TEM). Color, viscosity and the thermostability of these adhesives with nano-clay were also evaluated. First, AFM and TEM studies showed adequate dispersion and impregnation of nano-clay. The viscosity of PVAc adhesive was not affected by the incorporation of nano-clay, whereas the UF adhesive was. With both PVAc and UF adhesives, the presence of nano-clay increased the L^⁎ and b^⁎ color parameters, especially when 1.5 wt% nano-clay was used. The incorporation of the nano-clay improved thermostability, as determined by thermogravimetric analysis (TGA). Finally, it was shown that the nano-clay incorporation improved SS and PWF. The highest values of SS were obtained when nano-clay was added at 1.5 wt% concentration in the PVAc adhesive under dry conditions. SS was not affected by nano-clay addition in the UF adhesive under dry conditions. However, under wet conditions, both 1.0 and 1.5 wt% loadings of nano-clay increased SS with both adhesive types. The addition of nano-clay in both proportions increased PWF by approximately 15% and between 20–30% in dry and wet conditions, respectively, for the PVAc adhesive. For the UF adhesive, PWF increased by approximately 10% under dry conditions and 25–50% in wet conditions.     

Bond quality at the FRP–wood interface using wood-laminating adhesives

Fibre-reinforced polymer (FRP)-strengthened glulam would be a more economically viable product if a single adhesive type could be utilised at all the bonded interfaces. This paper describes a test programme that examines the hygrothermal compliance of five commercial wood-laminating adhesives when bonding commercially viable FRP materials to wood. It was seen that the integrity of the bond depended not only on adhesive type but also on the FRP type under consideration. For one of the FRP types, moisture-cycled FRP–wood bonded specimens obtained high wood failure percentages and good shear strength results that compared well with non-moisture-cycled FRP–wood specimens, non-moisture-cycled wood–wood bonded specimens and solid control specimens taken from the same board. This encouraging result suggests an alternative to the expensive structural epoxy adhesives, which are generally accepted as the appropriate adhesive in FRP-strengthened glulam.     

Bacterially derived biopolymers as wood adhesives

The wood adhesive market is very large and problems due to volatile organic compounds and toxic chemicals in many adhesives and their production are significant. In addition, most of the adhesives are derived from depleting petrochemical resources. An environmentally friendly wood adhesive based on renewable resources and produced by microbial fermentation has been explored. Using the shear block test method, a microbially produced polysaccharide has been tested and the effects of wood type, humidity, set time, partial acetylation, and surface wetting agents were determined. Shear strength of the microbial polysaccharide adhesive was compared to that of a commercial wood adhesive and other polysaccharides. Shear strengths of up to 20 MPa (3000 psi) for bonding maple have been obtained at 53% relative humidity and 22°C.     

Activating pulp toward acetylation by chemical or mechanical means

Activation of pulps during acetylation, by prior mechanical or chemical treatment, has been investigated. The effect of degree of beating on the acetylation rate of wood and bagasse pulps has been studied. It is found that the acetylation rate of pulps increases when the degree of beating of pulps is increased to a definite degree, after which it slows down. The maximum reactivity of bagasse pulp is obtained at 50°SR, while that of wood pulp is observed at 30°SR. The effect of grafting of acrylonitrile onto bagasse and wood pulps on their reactivity during acetylation has been also studied. The results indicate that grafting of acrylonitrile onto pulps has a favorable effect on their acetylation rate. This is dependent on the degree of grafting as well as the origin of pulp fibers. The most suitable method of activation during acetylation reaction is dependent on the origin of the pulp. The reactivity of bagasse pulp during acetylation is influenced more by beating of pulp, prior to the reaction, than by the grafting of acrylonitrile onto pulp. On the other hand, the acetylation reaction of wood pulp is activated by grafting rather than by beating. Also the effect of the activation process, mechanical or chemical, on the strength properties of the paper sheets produced from acetylated pulps has been investigated. Chemical activation of wood pulp prior to acetylation resulted in pulp with slightly higher strength properties than that activated by mechanical means. But, in the case of bagasse pulp, mechanical activation resulted in a pulp with strength superior to that produced by chemical activation.     

Comparative study of zein- and gluten-based wood adhesives containing cellulose nanofibers and crosslinking agent for improved bond strength

Many of the currently used wood adhesives contain chemicals that are harmful to human health and the environment. Increasing environmental and human health concerns have made the development of safe biobased adhesives a priority. In this study, two plant proteins, i.e., zein and wheat gluten, were used to develop wood adhesives and their performance was compared through simple lap shear tests and plywood flexural/internal bond tests in dry and wet conditions. To increase their bond strength, cellulose nanofibers were added to create nanocomposite adhesives and glutaraldehyde was also used to crosslink the proteins. Single-lap shear test was performed to measure the bond strength of different adhesive formulations and determine the optimal formulations and processing conditions. Fractured bond surfaces were studied using optical observation and scanning electron microscopy to determine bond failure mechanisms. Thermal and chemical properties of the adhesives were evaluated using thermogravimetric analysis and Fourier transform infrared spectroscopy, respectively. The bond strength of both zein and gluten adhesives was significantly increased by the addition of the cellulose nanofibers and/or glutaraldehyde, although the two adhesives responded differently to the two reinforcement materials due to the different solvents used to prepare the adhesives. The bond failure mode changed from cohesive failure of the adhesive to structural failure of the adherent for the gluten adhesive containing CNFs and glutaraldehyde. Potential zein and gluten adhesive formulations were used to produce plywood samples and their performance was assessed under different conditions. The formulations with industrial potential were discovered through this study.     

Effect of Adhesive Thickness on Joint Strength: A Molecular Dynamics Perspective

Recent studies suggest that adhesion in thin joints depends on several factors including temperature, interface toughness, strain rate, surface roughness of adherends, bondline thickness of adhesives, and many others. Influence of thickness on joint properties is surprising but experimentally well documented without reasonable explanations. In this study, we attempt to address the mechanical behavior of polymer adhesives by molecular dynamics (MD) simulation. We show that interfacial strength of the joints in tensile, shear, or combined loading significantly depends on the coupling strength between adhesives and adherends. Failure of joints is always at the interface when coupling strength is weaker. With stronger interfaces, cohesive failure occurs by cavitation or by bulk shear depending on the loading condition. When joints are loaded in tension, it requires an exceedingly stronger interface to realize pure shear failure, otherwise failure is through interface slip. Under a mixed mode condition, interface slip is difficult to avoid. As long as failure is not at the interface alone, the yield strength of joints improves significantly with the reduction of thickness. Increase in bulk density and change in polymer configurations with the reduction of adhesive thickness are believed to be the two key factors in improving mechanical behavior of adhesives.     

Soy proteins as plywood adhesives: formulation and characterization

Soybean proteins have great potential as bio-based adhesives. The objectives of our study were to develop and characterize formaldehyde-free soybean wood adhesives with improved water resistance. Second-order response surface regression models were used to determine the effects of soy protein isolate concentration, sodium chloride, and pH on adhesive performance. All three variables affected both dry and wet strengths of bonded wood specimens. The optimum operation zone for preparing adhesives with improved water resistance is at a protein concentration of 28% and pH 5.5. Sodium chloride had negative effects on adhesive performance. Soy adhesives modified with 0.5% sodium chloride had dry strength, wet strength, and boiling strength of bonded specimens comparable to nonmodified soy adhesives. Rheological study indicated that soy adhesives exhibited shear thinning behavior. Adhesives modified with sodium chloride showed significantly lower viscosity and yield stress. Sodium chloride-modified soy adhesives formed small aggregates and had low storage moduli, suggesting reduced protein–protein interactions. These formaldehyde-free soy adhesives showed strong potential as alternatives to commercial formaldehyde-based wood adhesives.