水性环氧树脂包覆有机蒙脱土制备木材胶粘剂

摘要：水性环氧树脂通常含有水溶性分子或分子链，导致在高温和潮湿条件下作为木材胶粘剂时耐水性及力学性能较差。采用有机改性的纳米蒙脱土改性水性环氧树脂增强水性环氧树脂胶粘剂的耐水性及力学性能。并通过乳液包覆蒙脱土的方法与直接共混的方法对比，研究了不同添加量有机蒙脱土（0%，3%，6%，9%）对胶粘剂性能的影响。胶粘剂的耐水性及力学性能通过测量胶粘剂在干燥及潮湿条件下的剪切强度来表示。通过TGA、SEM、TEM、DSC研究了复合胶粘剂的热稳定性和结构。结果表明，在水性环氧树脂中添加有机改性的纳米蒙脱土，可以有效地提高胶粘剂的粘结强度，此外，采用乳液包有机覆蒙脱土的方法比直接共混的方法制备得到胶粘剂，有机蒙脱土在胶粘剂中分布更均匀，具有更优异的力学性能，说明有机蒙脱土在复合材料中的分散质量是影响复合胶粘剂性能的主要原因。     

Greener adhesives based on UF/soy protein reinforced with montmorillonite clay for wood particleboard

There is a global concern about the types of adhesives used for the binding of wood particles, most of which include formaldehyde in their formulation. The aim of this work is to study the effect of raw montmorillonite (Mt) particles on blended urea formaldehyde (UF)/soy protein (SP) adhesives for the manufacture of wood particleboards to reduce the use of this carcinogenic component. Rheology showed that Mt does not alter the viscosity of adhesives at high shear rates, so they can be applied by spray. Thermogravimetric analysis/derivative thermogravimetry (TGA/DTG) analysis revealed an enhancement of their thermal stability due to the presence of clay particles. Polymer–Mt interaction was studied by small amplitude X-ray scattering and scanning electron microscopy. According to these results, the exfoliated structure of the clay particles was achieved. Wood particleboards were manufactured with UF/SP/Mt adhesives in order to study their mechanical properties. The three-point bending test showed that Mt particles improved the modulus of both rupture and elasticity. UF/SP/Mt resins proved to be a prominent product for the development of environmentally friendlier particleboards with desirable mechanical properties.     

Physical,mechanical properties,and structural characterization of konjac glucomannan-chitosan-polypeptide adhesive blends

Polypeptide was used to improve the water resistance of konjac glucomannan (KGM)-chitosan-based wood adhesives. With identical solid content, the tensile strength in wet state was increased by the addition of polypeptide and a maximum tensile strength of 2.34 MPa was reached. To examine the physical and chemical changes induced by the addition of polypeptide, the structure, viscoelasticity, morphology, and miscibility of the adhesive blends were determined by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, rheometry, and scanning electron microscopy. Results indicated improvements in mechanical properties were related to the formation of intermolecular hydrogen bonds and covalent bonds between KGM, chitosan, and polypeptide, which was enhanced by increasing the polypeptide concentration. Good miscibility existed between KGM, chitosan and polypeptide, as well as good wettability between the adhesive blends and wood veneer.     

Influence of the filler material on the thermal stability of one‐component moisture‐curing polyurethane adhesives

Filler materials are part and parcel for the adjustment of adhesives, in particular, their rheological and mechanical properties. Furthermore, the thermal stability of adhesives can be positively influenced by the addition of an expedient filler, with inorganic types common practice in most cases. In this study, one‐component moisture‐curing polyurethane adhesives for engineered wood products based on isocyanate prepolymers with different polymer‐filled polyether polyols were investigated with regard to the filler's potential to increase the thermal stability of bonded wood joints. The property changes due to the addition of fillers were determined by means of mechanical tests on bonded wood joints and on pure adhesive films at different temperatures up to 200°C. Additional analyses by atomic force and environmental scanning electron microscopy advanced the understanding of the effects of the filler. The tested organic fillers, styrene acrylonitrile, a polyurea dispersion, and polyamide, caused increases in the cohesive strength and stiffness over the whole temperature range. However, the selected filler type was hardly important with regard to the tensile shear strength of the bonded wood joints at high temperatures, although the tensile strength and Young's modulus of the adhesive films differed over a wide range. Prepolymers with a lower initial strength and stiffness resulted in worse cohesion, in particular, at high temperatures. This disadvantage, however, could be compensated by means of the filler material. Ultimately, the addition of filler material resulted in optimized adhesive properties only in a well‐balanced combination with the prepolymer used. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Cottonseed protein-based wood adhesive reinforced with nanocellulose

Although protein-based adhesives are eco-friendly, sustainable, and biodegradable, continued improvement in their adhesive performance is desirable. In this work, the effect of adding nanocellulose particles to cottonseed protein-based wood adhesives was studied. Cellulose nanofibers (CNF) were found to be most beneficial at about a 2% additive level, giving 22% improvement in dry adhesive strength over the cottonseed protein control. Cellulose nanocrystals (CNC) were optimal at about 10% additive level, giving 16% strength improvement relative to cottonseed protein alone. The hot water resistance of cottonseed protein isolate was also improved with CNF addition, but not with CNC addition. For comparison, soy protein isolate was also studied and showed about the same relative dry strength improvements with nanocellulose addition, but improvement of hot water resistance was less apparent. Infrared and thermogravimetric analysis suggested that the protein and the nanocellulose were interacting with each other. Thus, CNF may be a useful additive to cottonseed protein formulations used as wood adhesives.     

Structural Adhesives Modified with Thermally Expandable Particles

In this study, the behaviour of two structural adhesives modified with thermally expandable particles (TEPs) was investigated as a preliminary study for further investigations on the potential of TEPs in adhesive joints. Tensile bulk tests were performed to get the tensile properties of the adhesives and TEPs-modified adhesives. In order to determine the expansion temperature of the particles while encapsulated in these particular adhesive systems, the variation of the volume of adhesive samples modified with different TEPs concentration as a function of temperature was measured. Further, the possibility of any chemical interactions between TEPs and adhesives matrix in the TEPs-modified specimens was verified by a Fourier transform infrared spectroscopy analysis. Finally, the fracture surfaces of the unmodified and TEPs-modified specimens, as well as the dispersion and the morphology of the particles, were examined by a scanning electron microscopy analysis. It was found that the stiffness of the TEPs-modified adhesives is not affected by incorporation of TEPs in the adhesives matrix, while the tensile yield strength decreased by increasing the wt% TEPs content. In applications of such particular materials (TEPs-modified adhesives), the temperature should be controlled to stay between 90°C and 120°C in order to obtain the highest expansion ratio. At a lower temperature, not all the particles will expand, and above, the TEPs will deteriorate and as a result the TEPs-modified adhesives will deteriorate.     

Some Aspects of Bond Formation and Failure in Adhesive Wood Joints

An investigation has been made of the effect of varying glue-spread on the bond strength of holly (Ilex aquifolium) using three adhesives and three different wood sections. The glue-spreads are lower than those normally used, and it has been found with edge-grain joints that 100% cohesive wood failure can occur with a glue-spread as low as 2.7mg/cm². Scanning electron microscopy shows that interlocking between adhesive and adherend does not occur. Factors leading to delamination and joint failure are discussed.

Lignin, without further addition, has been shown to be a useful wood adhesive. It has also been shown that it is possible to make end-grain joints without the use of an adhesive; the lignin present in the wood specimens is considered to be responsible for such joints.     

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     

Multi-scale evaluation of the effects of nanoclay on the mechanical properties of wood/phenol formaldehyde bondlines

Nanoclay is a natural mineral that has great potential as a reinforcing filler in wood adhesives. In order to investigate the reinforcing mechanism more clearly, the crystalline structure, chemical properties, morphology, and thermal stability of pure PF and organic nanoclay-reinforced phenol formaldehyde (PF-OMMT) adhesive were characterized. The comparative mechanical properties of pure PF adhesive and PF-OMMT in the bondlines of plywood were analyzed by nanoindentation (NI) under different service environments and the shear strain distribution on the interphase was also measured by a digital image correction technique (DIC). X-ray diffraction (XRD), Fourier transform infrared (FTIR) and transmission electron microscopy (TEM) results indicated good dispersion of the clay in the PF matrix. The modified adhesive showed greater thermal stability than did the control adhesive, as evaluated by thermo-gravimetric analysis (TGA). The good dispersion of nanoclay and the positive effects of the nanoclay on the adhesive's water and heat resistance may have contributed to the improved mechanical properties of adhesives in an accelerated durability test. Compared to pure PF, the reduced elastic modulus and hardness of PF-OMMT in the bondline increased significantly and the strain distribution was much more uniform, resulting in an observed increase of macro-bonding strength of plywood, especially under conditions of severe cyclic water saturation and drying.     

Soy-oil-based waterborne polyurethane improved wet strength of soy protein adhesives on wood

Soy-oil-based waterborne polyurethane (WPU) is used to improve wet strength in shear test of wood bonded with an adhesive of soy protein isolate (SPI) by dispersing WPU into SPI slurry. WPU׳s effects on the physiochemical properties of WPU-SPI adhesives are characterized through Fourier transform infrared spectrum, transmission electron microscopy, thermal analysis, contact angle, and mechanical strength. Wet strength of the WPU-SPI adhesives increases by 65% compared to SPI control. Moreover, the microstructure of WPU has effects on the interactions between WPU and SPI. In this study, smaller and more uniform distributed WPU0002 is easier to interact and form stronger crosslinking network with protein than WPU0500. The stronger interaction between WPU0002 and protein results in increased viscosity and bond strength. The WPU-SPI blended adhesives show significantly improved wet strength, demonstrating their potential as wood adhesives.     

Some Aspects of Bond Formation and Failure in Adhesive Wood Joints

An investigation has been made of the effect of varying glue-spread on the bond strength of holly (Ilex aquifolium) using three adhesives and three different wood sections. The glue-spreads are lower than those normally used, and it has been found with edge-grain joints that 100% cohesive wood failure can occur with a glue-spread as low as 2.7mg/cm². Scanning electron microscopy shows that interlocking between adhesive and adherend does not occur. Factors leading to delamination and joint failure are discussed.

Lignin, without further addition, has been shown to be a useful wood adhesive. It has also been shown that it is possible to make end-grain joints without the use of an adhesive; the lignin present in the wood specimens is considered to be responsible for such joints.     

Addition of Urethane-Based Thickener to Waterborne Polyurethane Adhesives Having Different NCO/OH Ratios and Ionic Groups Contents

Several waterborne polyurethane adhesives containing different hard-to-soft segment ratios and ionic groups were prepared by using the acetone process. To improve the rheological properties, a 5 wt% of hydrophobically-modified ethoxylated urethane-based thickener (HEUR) was added. The adhesives were characterized by shear rate-controlled rheology, pH, particle size measurements, solids content and laser confocal microscopy. The adhesive films were characterized by plate–plate rheology, dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). The adhesion properties were measured using T-peel tests of leather/thickened polyurethane adhesive/SBR rubber joints. The addition of the HEUR thickener produced an improvement in rheological properties of polyurethane adhesive dispersions as a result of the physical interactions between the polyurethane particles and the thickener. The addition of the HEUR thickener markedly increased the viscosity of the polyurethane adhesives, as the hard-to-soft segments ratio decreased and the ionic groups content in the polyurethane increased. As the hard segment content of the thickened polyurethane adhesive decreased, the kinetics of crystallization was favoured as a result of stronger polyurethane/thickener interactions. As a result, an improvement in the adhesive strength in the leather/thickened polyurethane adhesive/SBR rubber joints was obtained.     

Glutaraldehyde-wheat gluten protein adhesives for wood bonding

ABSTRACT

Wheat gluten protein hydrolysate was used as a biomass feedstock to prepare environmentally friendly protein-based adhesives, with hydrolyzed wheat protein as control. Glutaraldehyde was used to modify it to obtain a glutaraldehyde-wheat protein (GP) adhesive. Polyethylenimine (PEI) was also used as a crosslinking agent. Plywood has been prepared and tested, and its performance was used to measure the wheat gluten protein hydrolysate adhesive bonding performance. Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to analyze the adhesive thermal properties and the microstructures of the cured adhesives by scanning electron microscopy (SEM). The results show that modification by glutaraldehyde can effectively improve the bonding performance of wheat protein adhesives, the plywood bonded strength having been improved by its addition. The effect of PEI as a crosslinking agent became evident. It can greatly improve the bonding properties of glutaraldehyde-modified wheat protein adhesives. TMA analysis indicates that the glutaraldehyde-modified GP adhesive has a higher storage modulus than the unmodified one. The modulus of the adhesive increased after adding the PEI cross-linking agent.     

Improvements of the structural,thermal, and mechanical properties of structural adhesive with functionalized boron nitride nanoparticles

Investigations on the production and development of nanoparticle-reinforced polymer materials have been attracted attention by researchers. Various nanoparticles have been used to improve the mechanical, chemical, thermal, and physical properties of polymer matrix composites. Boron compounds come to the fore to improve the mechanical and thermal properties of polymers. In this study, mechanical, thermal, and structural properties of structural adhesive have been examined by adding nano hexagonal boron nitride (h-BN) to epoxy matrix at different percentages (0.5, 1, 2, 3, 4, and 5%). For this purpose, nano h-BN particles were functionalized with 3-aminopropyltriethoxysilane (APTES) to disperse the h-BN nanoparticles homogeneously in epoxy matrix and to form a strong bond at the matrix interface. Two-component structural epoxy adhesive was modified by using functionalized h-BN nanoparticles. The structural and thermal properties of the modified adhesives were investigated by scanning electron microscopy and energy dispersion X-ray spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. Tensile test and dynamic mechanical analysis were performed to determine the mechanical properties of the adhesives. When the results obtained from analysis were examined, it was seen that the nano h-BN particles functionalized with APTES were homogeneously dispersed in the epoxy matrix and formed a strong bond. In addition that, it was concluded from the experimental results that the thermal and mechanical properties of adhesives were improved by adding functionalized nano h-BN particles into epoxy at different ratios.     

Shear Refinement of Formaldehyde-Free Corn Starch and Mimosa Tannin (Acacia mearnsii) Wood Adhesives

The aim of this work was to reduce the viscosity of formaldehyde-free corn starch–mimosa tannin wood adhesives, without adversely affecting the mechanical properties of the product. The reduction of viscosity was achieved using shear refinement. The study focused on the physical phenomena before cross-linking of the wood adhesive. The physical (rheological characterization) and mechanical (bond strength) properties of formaldehyde-free corn starch and mimosa tannin wood adhesives were measured. The results showed that the shear refinement (290 rpm and 5 min, optimal conditions) reduced the viscosity of the corn starch–mimosa tannin wood adhesives (from 100 000 to 458 Pa s) with the advantage of being stable over time. Mechanical tests showed that the shear refinement did not influence the mechanical properties of corn starch–mimosa tannin wood adhesives.     

Nano boron nitride/polyurethane adhesives in flexible laminated food packaging: Peeling resistance and permeability properties

Polymeric multilayer films are widely used in food packaging due to their versatility. However, there are still some properties that might be improved, such as gas and vapor barrier behaviors. The incorporation of boron nitride into polymer matrixes is emerging as a potential method for the improvement of barrier properties due to its lamellar structure. In this context, our work investigates the addition of boron nitride into a bicomponent reactive polyurethane (PU), which could be used as an adhesive and improve the barrier layer. This material could be used as an alternative to aluminum foil in food packaging. Different concentrations of two different sizes of boron nitride (BN) particles were added to the PU adhesive: micro-structured boron nitride (BNm) and nano-structured boron nitride (BNn). The aim was to investigate the influence on the barrier properties against moisture and the peeling resistance. Field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) were performed to characterize the boron nitride samples. The effect of BNm or BNn addition on the glass transition of the nanocomposites was investigated by differential scanning calorimetry (DSC). Barrier properties were measured by a water vapor permeation test and the practical adhesion of laminates with BN/PU adhesives was characterized using peeling tests. The nanocomposites achieved reduction in water vapor permeance of up to 50% and a 37% increase in mechanical adhesion properties compared to the PU adhesive. The results revealed the high potential of boron nitride/PU adhesives for food packaging applications.     

Influence of the Chemical Structure of Urethane-Based Thickeners on the Properties of Waterborne Polyurethane Adhesives

To analyse the parameters that influence the thickening mechanism of waterborne polyurethane adhesives, different hydrophobically modified ethoxylated polyurethane based thickeners (HEUR) were used. The thickeners were characterized by proton nuclear magnetic resonance (¹H-NMR) and gel permeation chromatography (GPC). The thickened adhesive solutions were characterized by flow rheology, pH, particle size measurements, solids content, and confocal microscopy. The thickened solid adhesive films were characterized by ATR-IR spectroscopy, parallel plate rheology, dynamic mechanical thermal analysis (DMTA), and differential scanning calorimetry (DSC). The adhesion was measured by a T-peel test of leather/polyurethane adhesive/SBR rubber joints. The addition of the different HEUR thickeners increased the viscosity of the polyurethane dispersion to different degrees. Furthermore, whereas the un-thickened polyurethane dispersion showed a Newtonian rheological behaviour, a shear-thinning rheological behaviour was observed in the thickened dispersions due to thickener-thickener and polyurethane-thickener interactions. The viscosity of the thickened polyurethane adhesive solutions increased with the degree of hydrophobicity and the molecular weight of the thickener. The addition of different thickeners increased the pH values due to the ionic adsorption, which is one of the interactions that contribute to the thickening mechanism of the polyurethane thickeners, besides hydrogen bonding and van der Waals hydrophobic interactions (micelles). The entanglement of the thickened polyurethane adhesives was studied by confocal microscopy. Although the addition of the thickeners did not affect the thermal properties of the polyurethanes, the T-peel strength of leather/adhesive/SBR rubber joints was influenced by the rheological properties of the thickened adhesives.     

采用DSC和FTIR对木材和API胶粘剂间反应的研究

采用差示扫描星热法(Differential Scanning Calormelry,简称DSC)和傅立叶变换红外吸收光谱(Fourier Transform Infrared Spectroscopy,简称FTIR)对木材和水性高分子异氰酸酯胶粘剂(Aqueous Polymer Isocyanate,简称API)的胶接机理进行了研究。DSC和FTIR的试验结果均表明:API胶粘剂和木材间发生了化学反应:API胶粘剂和木材间发生的反应所需活化能远小于API胶粘剂的主剂+固化剂的活化能,亦即用API 胶粘剂胶接木材时发生的反应要比API胶粘剂本身的固化反应容易得多,同时从理论上证明使用API胶粘剂胶接木材时装配时间最长不应超过其活性期的一半时间,且装配时间越短越好;文中还研究了升温速率对API胶粘剂DSC图谱的影响。     

Improving electrical and mechanical properties of a conductive nano adhesive

In this experimental study, lap shear strength and electrical conductivity of nanohybrid adhesives containing multi-walled carbon nanotubes (MWCNT) and silver (Ag) nanoparticles were investigated. Ag nanoparticles were produced via arc-discharge method in liquid nitrogen. For characterizing the Ag nanoparticles, X-ray diffraction analysis, transmission electron microscopy, and scanning electron microscopy (SEM) were performed. Tensile lap shear properties were determined in accordance with ASTM D 1002-10 standard. Mechanical and the electrical properties of nanohybrid adhesives were compared with neat epoxy adhesive. The best electrical conductivity of nanohybrid adhesive was obtained for the 1% wt MWCNT-2% wt Ag-contained sample. However, the samples which contain 0.5% wt. MWCNT–0.5% wt. Ag nanoparticles reached the highest lap shear strength. The results showed that Ag nanoparticles enhance the conductivity in the presence of MWCNT. It is concluded that the MWCNT act as conductivity bridges among epoxy adhesive and facilitate the electron transfer. As seen in the tensile test results, the ductility of the adhesive was improved by adding the nanoparticles in to the epoxy resin.