Elastic properties of adhesive polymers. III. Adhesive polymer films under dry and wet conditions characterized by means of nanoindentation

The mechanical properties of cured wood‐adhesive films were tested in dry and wet states by means of nanoindentation. A fluid cell was used to monitor possible property changes as a function of changing moisture content. Under wet conditions, the elastic modulus and hardness of all tested adhesives (i.e., urea formaldehyde, melamine urea formaldehyde, phenol resorcinol formaldehyde, and one‐component polyurethane) were reduced to about half of their values in the dry state. After renewed drying, all adhesives largely recovered their initial mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

The role of wood extractives in structural hardwood bonding and their influence on different adhesive systems

Bonding of hardwood for structural applications is a complex process. Various factors influence the bond performance and the interface area is considered the most crucial part. The chemical composition of the interface, e.g. wood extractives, is expected to influence the bonding of hardwoods. The subject of this study was to determine the influence of seven model substances that represent common wood extractives on different adhesive systems namely one-component polyurethane, two-component polyurethane, melamine urea formaldehyde and phenol resorcinol formaldehyde. The influence of the model substances on the cross-linking behavior of the adhesives was determined by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and on the rheological properties in terms of gel point and storage modulus. In addition, model substances characteristic for selected wood extractives were applied to the surface of European beech wood [Fagus sylvatica L.] before bonding and consequently tested in tensile shear mode according to EN 302-1. The ATR-FTIR spectra showed an influence of some substances on the crosslinking for all adhesive systems. Further, the curing process was mostly accelerated for phenol resorcinol formaldehyde, while melamine urea formaldehyde and polyurethane showed a less negative change in rheological behavior. The mechanical strength of beech wood bonds at room climate indicated only minor influence of model substances, but samples tested in wet conditions demonstrated a significant effect on some adhesive systems. It was concluded, that polyurethane adhesives degrade by acid substances and melamine urea formaldehyde by starch and gallic acid. Phenol resorcinol formaldehyde system was influenced negatively by starch and acids.     

A novel wood‐binding domain of a wood–plastic coupling agent: Development and characterization

Poly(N‐acryloyl dopamine) (PAD) was successfully synthesized through free‐radical homopolymerization of N‐acryloyl‐O,O′‐diphenylmethyldopamine and subsequent deprotection. The adhesive ability of PAD to wood was studied in detail. PAD underwent substantial oxidation and crosslinking reactions at about 80°C. Therefore, maple veneer samples bonded with PAD powder at a press temperature of 120°C had high shear strength and high water resistance. In contrast to conventional wood adhesives such as phenol‐formaldehyde and urea‐formaldehyde resins, PAD resulted in an increase, rather than a decrease, in the shear strengths of two‐ply laminated maple veneer test specimens that had undergone a water soaking and drying treatment. A mixture of PAD and polyethylenimine (PEI) resulted in much higher shear strength than PAD alone. To achieve high shear strength and high water resistance, the maple specimens bonded with PAD–PEI mixtures had to be cured above 150°C because reactions between PAD and PEI occurred at about 150°C. The water resistance of the maple specimens bonded with the PAD–PEI mixtures was dependent on the PAD:PEI weight ratio and the curing temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1078–1084, 2003     

Low addition of melamine salts for improved melamine‐urea‐formaldehyde adhesive water resistance

The addition of melamine acetate salts to an adhesive glue mix can allow the use of melamine–urea–formaldehyde (MUF) resins of lower melamine contents (rather than just urea–formaldehyde resins) and lower total amounts of melamine. Performances can be obtained that are characteristic of the top‐of‐the‐line, generally higher melamine content MUF adhesive resins for the preparation of wood particleboard panels. Improvements in the panel internal‐bond strength of greater than 30% can be obtained by the addition of melamine acetate salts to top‐of‐the‐line MUF resins. The approach to the concept of increased melamine solubility with a melamine salt is compatible with the approach of increasing melamine solubility with solvents such as acetals (e.g., methylal). However, the synergy advantage of using the two approaches jointly is not very marked. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 287–292, 2003     

Adhesive bonding of acetylated wood

Eighteen thermoplastic and thermosetting adhesives, including emulsion polymer-isocyanates, polyurethane, moisture-curing hot-melt, polyvinyl acetates, neoprene and waterborn contacts, casein, epoxy, melamine, ureas, resorcinol, phenol-resorcinols, and phenolics, were tested for their adhesion to yellow-poplar wood acetylated to 0, 8, 14 and 20 weight percent gains. Effectiveness of adhesion was determined by measuring shear strength and wood failure in a dry condition and after saturation with water. Adhesion was reduced to varying degrees in proportion to the compatibility of the adhesive with the amount of non-pollar, hydrophobic acetate groups in the acetylated wood. Seven of the adhesives developed bonds of high integrity at all levels of acetylation when tested in the dry condition. Two room-temperature-setting adhesives, one a resorcinol-formaldehyde and the other a phenol-resorcinol-formaldehyde, together with a hot-setting acid-catalysed phenol-formaldehyde, developed bonds of high strength and resulted in wood failure at all levels of acetylation when tested in the water-saturated condition.     

Acetal‐induced strength increases and lower resin content of MUF and other polycondensation adhesives

Acetals such as methylal and ethylal are shown to be particularly effective additives in improving the strength of wood boards bonded with melamine‐ urea‐formaldehyde (MUF) resins, although they show some appreciable but lesser effect on other resins too, particularly phenol‐ formaldehyde resins. They equally allow a considerable decrease in resin loading, and thus, in melamine content, on the bonded wood panel and at parity of performance. Their development as additives is then primarily, but not only, targeted at the MUF adhesive resins. One‐third decreases in MUF adhesives loading at parity of performance or equally internal bond (IB) strength increases approximately up to 50% by addition of methylal are shown to be possible by laboratory particleboard as well as by thermomechanical analysis (TMA). The reasons for methylal and ethylal behavior were studied by a variety of techniques, including liquid‐ and solid‐ phase ¹³C‐NMR and could be mostly ascribed to the increased effectiveness and participation of the melamine to resin crosslinking due to its now preferentially homogeneous rather than heterogeneous reactions, consequences of the increased solubility in water afforded by the acetal cosolvents. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2561–2571, 2002     

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.     

Polyphenolic extracts of Pinus radiata bark and networking mechanisms of additive‐accelerated polycondensates

The use of various chemicals for extracting polyphenolic fractions (tannins) from Pinus radiata bark was examined with the aim of obtaining high yields of high‐quality tannins to be used as wood adhesives. Extractions carried out under very highly alkaline conditions (pH > 10.5) gave relatively high yields but also excessive viscosity values even in 30% (w/w) solutions, and this demonstrated their inability to function as wood adhesives. Solutions (30% w/w) of mildly extracted (pH < 8.3) fractions gave workable viscosity values and were used in a subsequent study. A rapid acceleration effect was observed in these fractions when ammonia was used as a catalyst. Solid‐state, cross‐polarization/magic‐angle‐spinning ¹³C‐NMR of the cured samples showed evidence proving the existence of benzyl amine bridging networks in their hardened state. Simultaneously accelerated copolymerization could be observed in phenol–resorcinol–formaldehyde/P. radiata bark tannin mixtures with the addition of ammonia, as indicated by viscosity measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2487–2493, 2007     

Low‐volatility acetals to upgrade the performance of melamine–urea–formaldehyde wood adhesive resins

1,1,2,2‐Tetramethoxyethane (TME), a high boiling point acetal derived from glyoxol, lhas been shown to upgrade the performance of melamine‐urea‐formaldehyde (MUF) and some UF resins used for wood adhesives. This affords the possibility of decreasing the percentage of resin used in the preparation of wood panels without volatilizing the TME acetal used.     

木材工业用胶粘剂的现状及发展趋势

主要介绍了脲醛树脂、酚醛树脂、三聚氰胺－ 甲醛树脂、木质素、单宁、异氰酸酯等木材工业用胶粘剂的研制状况及发展趋势。     

TTT and CHT curing diagrams of water‐borne polycondensation resins on lignocellulosic substrates

Lignocellulosic substrates such as wood were found to have a marked modifying influence on both lower temperature and higher temperature zones of TTT and CHT diagrams during hardening of phenol–resorcinol–formaldehyde (PRF) and melamime–urea–formaldehyde (MUF) polycondensates. Although the modifying influence of the substrate on the higher temperature zone of CHT diagrams presented the same trend of what was already reported for phenol–formaldehyde (PF) and urea–formaldehyde (UF) polycondensates, marked differences from what reported in the literature were recorded for TTT diagrams of all these polycondensates as well for the lower temperature zones of the CHT diagrams on lignocellulosic substrates, both of which had not been investigated previously. The chemical and physical mechanisms of the interactions of the resins, the substrate, and the water carrier causing such marked variations are presented and discussed. Although in the higher temperature zones both substrate and water carrier play an important role, in the lower temperature zone the presence of water appears to be the dominant factor causing the observed variations. The generalized modified CHT and TTT diagrams characteristic of the behavior of these water‐borne polycondensates on lignocellulosic substrates can be used to describe the behavior and complex changes of phase the formaldehyde‐based polycondensation resins undergo when used as wood adhesives during their curing directly in the wood joint. The results also show that diagrams obtained with pure resin cannot be used to predict the behavior of the polycondensate when this is markedly modified by the presence of interacting solvents and substrates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2128–2139, 2001     

Environmentally friendly mixed tannin/lignin wood resins

We obtained lignin‐based wood adhesives satisfying the requirements of relevant international standards for the manufacture of wood particleboard. These were based on two different low‐molecular‐mass lignins. These lignin‐based wood adhesives did not use any formaldehyde in their formulation; formaldehyde was substituted with a nonvolatile nontoxic aldehyde, namely, glyoxal. The last formaldehyde present, contributed by a fortifying synthetic phenol–formaldehyde resin, was also eliminated by the substitution of the phenol–formaldehyde resin with a natural, vegetable polyflavonoid tannin extract to which no aldehyde was added. This substitution brought the total content of natural material up to 80 wt % of the total adhesive. The adhesives yielded good internal bond strength results of the panels, enough to pass relevant international standard specifications for interior‐grade panels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure of resorcinol,phenol, and furan resins by MALDI‐TOF mass spectrometry and 13C NMR

The structure of traditional, linear phenol–resorcinol–formaldehyde (PRF) resins, urea‐branched PRF resins, and phenol–resorcinol–furfural (PRFuran) resins has been investigated in depth by both matrix‐assisted laser desorption/ionization time of flight (MALDI‐TOF) mass spectroscopy and ¹³C NMR. The structure of a variety of oligomers has been obtained, and the structures present in each of the three types of resins related to the very different percentages of resorcinol needed for their equal performance as adhesives. The oligomers type and species distribution appeared very different for each case. PRF resins performance is improved by maximizing either the proportion of resorcinol‐containing oligomers or methylol‐groups containing oligomers, even without any resorcinol, or both. It is equally obtained by the minimization of the relative proportion of the low reactivity Phenol (CH₂ Phenol) species in which resorcinol is not present, this being the most important parameter. This can be obtained by more effective use of the resorcinol by just modifying the resin manufacturing procedure. This parameter instead does not appear to be determinant in PRFuran resins. In these, it is the higher molecular weight of furfural in relation to formaldehyde that engenders for the same manufacturing procedure a correspondingly lower proportion of resorcinol in the resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2665–2674, 2004     

The chemistry and development of tannin/urea–formaldehyde condensates for exterior wood adhesives

Novolak-like materials were prepared by condensation of urea–formaldehyde resins with resorcinol and/or resorcinolic A-rings of polyflavonoids such as condensed tannins. The copolymers formed were used as thermosetting and cold-setting exterior-grade wood adhesives. Condensation of tannins with small amounts of urea–formaldehyde resins can prevent the water deterioration normally experienced by the latter resins. Conversely, urea–formaldehyde resins improve crosslinking and strength of wood tannin–formaldehyde networks.     

Co‐polymerization analysis of thermosetting resins using 1H‐15N‐13C triple resonance NMR spectroscopy

¹H‐¹⁵N‐¹³C correlation NMR spectroscopy techniques developed to identify and characterize co‐polymer fragments in melamine‐urea‐formaldehyde (MUF) and phenol‐urea‐formaldehyde (PUF) model systems have been applied to industrially prepared MUF, PUF, and phenol‐melamine‐formaldehyde (PMF) resins. The NMR data confirm that co‐polymers form in a commercially prepared MUF resin manufactured by Momentive Specialty Chemicals Pty. Ltd. Spectra from PUF model reactions were compared with those from a PUF resin and it was determined that PUF co‐polymers did not form in the resin prepared using typical temperature and pH. Finally, NMR spectroscopy was used to identify and characterize PMF co‐polymer bonds in a phenol‐melamine‐urea‐formaldehyde (PMUF) resin prepared using a procedure from Momentive Specialty Chemicals Pty. Ltd. With these NMR techniques in hand, it is now possible to relate co‐polymer structures to properties of commercial thermosets. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

杉木液化产物用于胶粘剂制备的研究

研究用少量的苯酚液化木材及其产物用于胶粘剂制备的方法,在硫酸催化剂作用下,用苯酚液化杉木木粉,得到木材液化产物.在液化产物中加入适量的甲醛和氢氧化钠溶液制备热固性酚醛树脂.压板测试结果表明,由木材液化产物所得树脂的干状胶合强度令人满意,但经蒸汽循环试验后,湿状胶合强度尚达不到JAS标准的要求,在下阶段工作中,需进一步研究木材液化产物胶粘剂的改性以提高其胶合耐久性.     

Medium‐density particleboards from rice husks and soybean protein concentrate

Rice husks are a valuable agricultural residue produced worldwide with potential applications as a wood substitute in particleboard manufacturing. In this work, the feasibility of producing medium‐density particleboards based on waste rice husks bonded with environmentally friendly adhesives from soybean protein concentrate was analyzed. The mechanical properties, internal bond strength, and water resistance of the obtained panels bonded with the homemade soybean protein concentrate adhesives were compared to those of boards glued with commercial adhesives such as phenol–formaldehyde and urea–formaldehyde resins. An alkaline treatment improved the gluing ability of the soybean protein concentrate. The mechanical properties of the alkali‐treated soybean protein concentrate were comparable to those determined for panels with urea–formaldehyde. The lower water resistance of the alkali‐treated soybean protein concentrate particleboards, compared with that of the formaldehyde‐based resins, was counterbalanced by the advantage of being more environmentally sound, which makes them suitable for applications for which the requirements for water resistance are not stringent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

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.