Differential scanning calorimetry of hydrolysed mangrove tannin

Mangrove‐bark‐tannin adhesives are potential substitutes for phenol–formaldehyde (PF) wood‐bonding adhesives which are derived from petroleum, a finite natural resource. However, mangrove‐bark‐tannin adhesive exhibits poor adhesive properties, including brittleness, poor wet strength, and poor wood penetration. These shortcomings are due to its high reactivity and structural features. To reduce these shortcomings, the structure of the adhesive was modified by subjecting tannin to (a) caustic hydrolysis and (b) consecutive acetic anhydride and caustic hydrolysis. The effectiveness of these hydrolyses was determined by using differential scanning calorimetry (DSC) to monitor the reaction and cure characteristics of hydrolysed and unhydrolysed tannin with formaldehyde. These hydrolyses resulted in lowering both the activation energy and collision frequency of the cure reaction. Consequently, the initial reactivity of tannin towards paraformaldehyde, which was usually very high, was reduced. The resulting longer reaction time enhanced the extent of reaction, as was evident in the increase in heat of reaction of the hydrolysed tannin. © 2000 Society of Chemical Industry     

Eco-Friendly Adhesives Based on Tannin and N,N-Bis(2-Hydroxy-Ethyl) Fatty Amides (HEFAs) from Non-Traditional Oils for Wood Bonding

Abstract

Wood adhesives were formulated using tannin and N,N-bis(2-hydroxyethyl) fatty amides (HEFAs). The natural tannin-based adhesives can be used to replace formaldehyde-based adhesive systems and thereby reduce formaldehyde and volatile organic compound (VOC) emissions from adhesives used for plywoods. Performance properties of the adhesively bonded wood joints viz., tensile strength, impact strength and chemical resistance were measured. N,N-bis(2-hydroxyethyl) fatty amides (HEFAs) from non-traditional oils were mixed with a pure tannin-based adhesive as a crosslinker, and this increased the tensile strength, impact strength and chemical resistance of wood joints. The results revealed that a high performance and eco-friendly adhesive system for wood can be successfully formulated using tannin and HEFA.     

A new source of natural adhesive: Acacia mangium bark extracts co-polymerized with phenol-formaldehyde (PF) for bonding Mempisang (Annonaceae spp.) veneers

Acacia mangium is a fast-growing dicotyledonous tree species and has become the dominating plantation in Malaysia. It was grown particularly as a raw material for veneer, pulp, and paper industries. The chemical properties test in this study showed that the A. mangium tree bark contains higher extractive content as compared to the wood portion (sapwood). Tannin extracts from A. mangium tree bark were found to be rich in phenolic compounds and had the potential to replace conventional phenol-formaldehyde (PF) adhesive used in the plywood manufacturing industry. Tannin adhesive (tannin-paraformaldehyde) prepared from A. mangium bark tannin by cross-linking with paraformaldehyde were used for bonding of Mempisang (Annonaceae spp.) plywood board. However, the resulting bonding strength using tannin adhesive was found to be only suitable for interior grade application. Further extension of its application for interior and exterior grade plywood could be achieved with addition of PF (co-polymerization with resol) during the production process. The optimized formulation of tannin adhesive consists of A. mangium solid extracts (90 parts), commercial PF (10 parts), and paraformaldehyde (3%). Results have shown that the plywood shear strength complies with the requirement for European norms EN 314-1 and EN 314-2:1993, which includes the dry test, cold water test, and the boiling test.     

Solvent Effects on High Temperature Polyimides and their Bonded Joints

Environmental stress crazing/cracking (ESCR/C) of adhesives under organic solvent exposure is a subject of great practical importance to adhesive end-users, especially in dealing with structural applications. In the past, the mechanical properties of several adhesive systems have been shown to degrade considerably after both prolonged and momentary exposure to solvents under a state of stress. In this study, the solvent resistance of three structural polyimide adhesives was studied, with respect to organic solvents that may come in contact with the adhesives during their service life. Initially, dog-bone samples of the resin systems were prepared, according to ASTM Standard D638-91a, and these were soaked in the solvents to obtain equilibrium solvent mass uptake curves. The solvents used in the study included acetone, methyl ethyl ketone (MEK) and ethylene glycol, among others. The equilibrated samples were then tested in a miniature tensile testing machine, to obtain stress-strain characteristics. Secondly, samples equilibrated in the solvents were held in a vacuum environment at 150°C (which is below the glass transition temperature of the adhesives) to desorb the solvent, and these were then tested to obtain residual properties. To study the durability of bonded joints under solvent exposure, Ti-6A1-4V/adhesive bonds were prepared and wedge tests were performed on them for periods up to several days in solvent baths. Based on the measured crack lengths, the strain energy release rate due to solvent-induced environmental stress cracking (G_ESC) was computed as a function of crack growth rate. The G_ESC measurements help quantify the durability of the bonded joints on exposure to the various solvents, and further help in ranking the adhesives in terms of solvent resistance.     

Adhesion Studies of Mixtures of Ethyl Cyanoacrylate with a Difunctional Cyanoacrylate Monomer and with other Electron-deficient Olefins

Alkyl cyanoacrylate instant adhesives are widely used because of their fast cure speed and versatility on a large number of substrates. Recent performance improvements, such as increased thermal resistance, resulted from the addition of latent acids and polymers, which do not copolymerize with the adhesive monomer, to the adhesive formulations. However, use of these additives can increase fixture time or reduce the final adhesive strength.

Two methods for possibly improving alkyl cyanoacrylate instant adhesives, without loss of cure speed or adhesive properties, could be either crosslinking the alkyl cyanoacrylate monomer with a dicyanoacrylate or copolymerizing it with a second 1, 1 disubstituted electron-deficient olefin. A crosslinker. 1,4 butanediol dicyanoacrylate (BDDCA) and two monofunctional monomers, diethyl methylenemalonate (DEMM) and N,N diethyl-2-cyanoacrylamide (DECA), were prepared, in good purity, for adhesion studies with ethyl cyanoacrylate (ECA). Crosslinking ECA with BDDCA does improve solvent resistance, as determined by solvent swelling experiments. Glass fixture times are approximately the same for ECA, crosslinked ECA, the pure monomers, and monomer mixtures with ECA, while steel fixture times are generally slower. Crosslinking ECA with BDDCA does not improve lap-shear adhesion, either at room temperature or after thermal exposure at 121°C. Lap-shear strength data, before and after heat exposure, revealed that the ECA/DEMM and the ECA/DECA monomer mixtures exhibit weaker lap-shear adhesive strength than ECA alone.     

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.     

Effect of water on the strength of rubber bonding with adhesives based on reactive oligomers

The effect of water redistribution between SKEPT-40 rubbers and reactive adhesives based on SKN-18KTR mixtures with ED-20 on the strength of adhesive compositions was studied. Water vapor sorption isotherms were measured. It was shown that the water content of rubbers during their scheduled conditioning at a humidity of 65–70% leads to the spontaneous redistribution of water between the substrate and the adhesive. This process is accompanied by the retardation of the formation of the adhesive network structure and, as a consequence, by a fall in the strength of adhesive joints. The mechanism of formation and failure of SKEPT-40-(SKN + ED-20) adhesive joints was revealed. A procedure for calculating the amount of water capable of redistributing between the elements of adhesive joints is proposed. Rubber conditioning parameters that ensure the required quality of bonding the rubbers with SKN-18KTR-ED-20 compositions were determined.     

Soy-based,tannin-modified plywood adhesives

In this research, two different types of commercial tannins, namely a hydrolysable tannin (chestnut) and a condensed flavonoid tannin (mimosa), were used to prepare two types of soy-based (soy flour (SF) and soy protein isolate) adhesives for making plywood. Thermogravimetric properties (TGA) and its derivative as function of temperature (DTG) of different soy-based adhesive were measured in the range 40°C–300°C. Thermomechanical analysis (TMA) from 25°C to 250°C was done for the different resin formulations. Duplicate three-ply laboratory plywood panels were prepared by adding 300 g/m² of the adhesives’ total resin solid content composed of SF or isolated soy protein (ISP), urea, chestnut, and mimosa tannin extracts with hexamine as hardener. Based on the results obtained, tannins can improve SF adhesion properties. The TMA showed that chestnut tannin extract appeared to react well with SF, while mimosa tannin extract appeared to react well with ISP. Matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry also showed that among other reactions, the soy protein amino acids reacted with the tannins. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannin modified adhesive.     

Effects of Pinus pinaster bark extracts content on the cure properties of tannin-modified adhesives and on bonding of exterior grade MDF

Phenol-urea-formaldehyde-tannin (PUFT) adhesives with different degrees of phenol substitution by Pinus pinaster bark tannins were thermally characterized by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). They were employed to prepare exterior grade Medium Density Fiberboards (MDF) according to European Standards. DMTA and DSC experiments showed, first, that the tannin-modified adhesives hardened in the low temperature range (30-110°C) and, second, that increasing the tannin content of the adhesives reduced the curing temperature, obtaining at least the same mechanical strength (stiffness) and higher curing enthalpies (ΔH) than the commercial phenolic resin. Although only the MDF boards made using the lowest viscosity tannin-modified adhesive (PUFT-10), with a 44% phenol replacement by tannin, met the outdoor requirements, all the other tannin-modified adhesives boards met the interior grade specifications. Among the board properties evaluated, the low value of thickness swelling after 24-h water immersion of MDF boards prepared using the PUFT-10 (6.6%) is particularly noticeable, which means an improvement of almost 50% compared to that of the commercial PF (12.6%).     

Combination of lignin polyol–tannin adhesives and polyethylenimine for the preparation of green water‐resistant adhesives

In this study, a green adhesive from renewable lignin and tannin was developed with polyethylenimine (PEI) with a method to improve the water resistance of the lignin/tannin adhesive. Lignin polyols were prepared through the liquefaction of oil‐palm empty fruit bunches. The characteristics of the adhesive samples were compared with those of a commercial phenol–formaldehyde resin. Three plywood specimens bonded with the new adhesive showed a very high tensile strength (63.04 MPa) and were very water resistant. The effect of the solid content of the adhesives on the tensile strength and gel time and various weight ratios of PEI on the tensile strength and water resistance of the plywood specimens were evaluated. Thermal stability tests revealed that the lignin polyol–tannin/PEI adhesives had a high heat resistance (360 °C). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43437.     

A Solder Alloy Filled Z-Axis Conductive Epoxy Adhesive

Epoxy adhesives filled with four different volume fractions of eutectic tin-bismuth solder alloy were prepared and the effect of filler content on the electrical and mechanical properties of these anisotropic electrically conductive adhesives was investigated. The results show that the adhesive containing the lowest amount of the filler alloy had the best combination of conductivity, insulation resistance and shear strength. The DSC-measurements suggested that the filler melts before the cure of the resin begins which allows the filler to wet and bond well to the conductors. This was verified by SEM/EPMA examinations. A temperature cycling test and high humidity, high temperature treatment were conducted on the best composite adhesive. The temperature variation had no effect on conductivity of the joints while humid and hot environment decreased the conductivity.     

Strength, deformation and relaxation of joints bonded with modified cyanoacrylate adhesives

The introduction of high molecular weight poly(methyl methacrylate) or poly(butadiene-co-acrylonitrile) into ethyl 2-cyanoacrylate produced viscous adhesives with a homogeneous or heterogeneous structure after cure. Steel joints bonded with these adhesives are shown to have improved tensile shear strength, deformability and stress relaxation of bonds compared with pure cyanoacrylate adhesive. Poly(methyl methacrylate)-modified adhesive is recommended for static load-bearing joints while poly(butadiene-co-acrylonitrile)-modified adhesive is more suited to cyclic or vibrating loads.     

The effect of primers on adhesive properties and strength of adhesive joints made with polyurethane adhesives

The paper presents selected aspects of the effect of primers on adhesive properties and strength of aluminium sheet adhesive joints, made using polyurethane adhesives. The strength of adhesive joints was determined based on two cure time variants: 15 and 64 h. It was found that the longer cure time at a humidity of 33% is more desired, as it leads to a substantial increase in strength of the tested adhesive joints. In addition, two variants of surface preparation were applied: degreasing and degreasing followed by the application of a primer (a pro-adhesive agent). It was observed that the primer application prior to the application of an adhesive leads to a significant increase in strength compared to the variant where the adhesive application is preceded only by degreasing. Moreover, the aluminium sheet surface that was subjected to cataphoretic painting and priming exhibits better adhesive properties. It has a higher value of both surface free energy and its dispersion and polar components compared to the surface that was only subjected to degreasing.     

Effect of using sepiolite silicate + fumed silica mixtures as fillers on the characteristics of solvent-based polyurethane adhesives

Abstract —Both fumed silica and sepiolite have been used as a filler of polyurethane (PU) adhesives. Although effective, the small particle size and the relative high cost of fumed silica are limitations in some applications. Sepiolite is cheaper than fumed silica, but its relatively large particle size facilitates its settling from the adhesive solutions. In this study, the usefulness of using sepiolite + fumed silica mixtures as a filler in solvent-based PU adhesives is demonstrated. The rheological and adhesion properties of the PU adhesive solutions and the rheological and mechanical properties of the PU films (without solvent) were studied. SEM micrographs of PU films showed the morphology and compatibility of the fillers with the PU matrix. The use of sepiolite + fumed silica mixtures inhibited the settlement of the filler from the PU adhesive solutions, increased both the storage and the loss moduli, and improved the rheological and mechanical properties of the PU. On the other hand, the green (immediate) T-peel strengths of roughened styrene-butadiene rubber/PU adhesive joints and plasticized PVC/PU adhesive joints were greatly improved in filled PU adhesives. The effects produced by using fumed silica alone or sepiolite + fumed silica mixtures were very similar, although in general, somewhat more marked in fumed silica-filled PU.     

A Solder Alloy Filled Z-Axis Conductive Epoxy Adhesive

Epoxy adhesives filled with four different volume fractions of eutectic tin-bismuth solder alloy were prepared and the effect of filler content on the electrical and mechanical properties of these anisotropic electrically conductive adhesives was investigated. The results show that the adhesive containing the lowest amount of the filler alloy had the best combination of conductivity, insulation resistance and shear strength. The DSC-measurements suggested that the filler melts before the cure of the resin begins which allows the filler to wet and bond well to the conductors. This was verified by SEM/EPMA examinations. A temperature cycling test and high humidity, high temperature treatment were conducted on the best composite adhesive. The temperature variation had no effect on conductivity of the joints while humid and hot environment decreased the conductivity.     

Reduction of formaldehyde emission from plywood

The aim of this work is to evaluate performances of tannin-based resins designed as adhesive in the plywood production. For this purpose, a part of phenol formaldehyde (PF) and melamine formaldehyde (MF) in the classic adhesive formulation was replaced by tannin. The physical properties of the formulated resins (rheological characterization, etc.) were measured. In order to analyze the mechanical performance of tannin-based resins, plywood panels were produced and the mechanical properties including tensile strength wood failure and three-point bending strength were investigated. The performance of these panels is comparable to those of plywood panels made by commercial PF and MF. The results showed that the plywood panels bonded with tannin–PF (PFT) and tannin–MF (MFT) resins exhibited better mechanical properties in comparison to the plywood panels made of commercials PF and MF. The introduction of small properties of tannin in PF and MF resins contribute to the improvement of the water performance of these adhesives. The formaldehyde emission levels obtained from panels bonded with tannin-based resins were lower than those obtained from panels bonded with control PF and MF. Although there are no actual reaction at all between PF, MF, and tannin, addition of tannin significantly improves the water resistance of PF and MF resins. This is a novel finding that manifests the possibility of replacing a convention PF and MF resins by tannin. Modified adhesive is one of the goals in the plywood production without changing any of their production conditions with improvement to their overall properties.     

Impact of multiwall carbon nanotubes on the fatigue strength of adhesive joints

This paper presents the results of research undertaken to determine the possibility of improving the fatigue properties of peel-loaded adhesive joints by dispersing multiwall carbon nanotubes (MWCNTs) into epoxy-based adhesives. The fatigue strength tests were carried out on an electromagnetic inductor with the resonance frequency of the adhesively bonded joint specimen. The tests were conducted for three types of epoxy adhesives whose properties were modified through the introduction of multiwalled carbon nanotubes, into their structure. Carbon nanotubes were synthesized by means of the Chemical Vapour Deposition (CVD) method with Fe-Co catalysts. A quantity of 1 wt.% of the dried material was dispersed into the epoxy adhesives. The results of the fatigue strength tests revealed a significant improvement of the fatigue lifetime of adhesive joints due to MWCNT introduction as filler for epoxy adhesives. In the case of the Epidian 57/PAC adhesive composition, a more than twofold increase in the fatigue lifetime was obtained (an increase of 106.8%). For the Bison Epoxy adhesive composition, the fatigue lifetime increased by 69.3%. The fatigue strength for the best result increased by about 13%.     

Effect of silicon carbide nanoparticles on the adhesion strength of steel–epoxy composite joints bonded with acrylic adhesives

This paper reports a study on the effect of silicon carbide nanoparticles on the adhesion strength of steel–glass/epoxy composite joints bonded with two-part structural acrylic adhesives. The introduction of nanosilicon carbide in the two-part acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strengths of the adhesive joints increased with adding the filler content up to 1.5?wt%, after which decreased with adding more filler content. Also, addition of nanoparticles caused a reduction in the peel strength of the joints. DSC analysis revealed that Tg values of the adhesives rose with increase in the nanofiller content. The equilibrium water contact angle was decreased for adhesives containing nanoparticles. SEM micrographs revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.     

结构胶胶接接头耐久性的研究进展

结构胶是胶黏剂中具有高强度、耐高温、高耐久特性的一类胶黏剂的总称,主要用于部件中承受载荷的胶接连接。胶接接头的耐久性能是结构胶应用中的一个重要指标。主要从影响胶接接头耐久性的内在因素和外在因素以及实验室研究方法对结构胶胶接接头耐久性的研究进展进行综述。     

Adhesive strength of steel–epoxy composite joints bonded with structural acrylic adhesives filled with silica nanoparticles

This paper reports a study on the effect of silica nanoparticles on the adhesion strength of steel–glass/epoxy composite joints bonded with two-part structural acrylic adhesives. The introduction of nano-silica in the two-part acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strengths of the adhesive joints increased with addition of the filler content up to 1.5 wt%, after which decreased with addition of more filler content. Also, addition of nanoparticles caused a reduction in the peel strength of the joints. Differential scanning calorimeter analysis revealed that T_g values of the adhesives rose with increasing the nanofiller content. The equilibrium water contact angle was decreased for adhesives containing nanoparticles. Scanning electron microscope micrographs revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.