Studies on the adhesion behavior of water-based adhesives blended with asan gum

The influence of asan gum, a locally available waste material obtained from the Terminalia alata tree, in blends with waterborne natural rubber adhesive and poly(vinyl acetate), on the lap shear strength and the peel strength has been investigated. Both the strength values increase, even with a small quantity of the gum. At a higher gum content, both these parameters, however, decrease. Fourier Transform Infrared studies reveal that there is no covalent bonding between the gum and the adhesives, although some hydrogen bonding exists in the poly(vinyl acetate) blend. Morphological studies reveal mechanical interlocking of the adhesive in the substrates. The pseudoplastic nature of the gum-modified waterborne adhesives has been confirmed from rheological studies using a Brookfield viscometer. The higher lap shear and peel strength values of the gum-modified adhesives compared to the control adhesives are attributed to the higher shear modulus of the former. The 100% modulus and tensile strength of the adhesives blended with the gum are also higher, compared to their controls.     

Reactive bonding of natural rubber to metal by a nitrile–phenolic adhesive

The mechanism of adhesive bonding of rubber to metal using an interlayer of bonding agent (adhesive) is discussed with respect to various physical and chemical events such as adsorption at the metal surface, chemical crosslinking within the adhesive, interdiffusion, and formation of interpenetrating networks at the rubber–adhesive interface. An investigation on the peel strength of a natural rubber (NR)–adhesive–metal joint, made by vulcanization bonding using nitrile–phenolic adhesive containing various concentrations of toluene diisocyanate–nitrosophenol (TDI–NOP) adduct, is presented. A single‐coat adhesive, consisting of a p‐cresol phenol formaldehyde resin, nitrile rubber (NBR), and vulcanizing agents in methyl ethyl ketone solvent, was selected for the study. Considerable improvement in the peel strength was obtained by the incorporation of TDI–NOP adduct into the nitrile–phenolic adhesive. The peel strength increases as the concentration of TDI–NOP adduct in the adhesive composition increases, then levels off with a transition from interfacial failure to cohesive tearing of rubber. The peel strength improvement is believed to be attributed to the interfacial reactions between the bonding agent and natural rubber, when TDI–NOP adduct is incorporated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2597–2608, 2001     

Carbohydrate Modfied Phenol-Formaldehyde Resins

Abstract

For adhesive self-sufficiency, the wood industry needs new adhesive systems in which all or part of the petroleum-derived phenolic component is replaced by a renewable material without sacrificing high durability or ease of bonding. We tested the bonding of wood veneers, using phenolic resins in which part of the phenol-formaldehyde was replaced with carbohydrates. Our experiments show that the addition of non-reducing carbohydrates and various polyols to phenol-formaldehyde resol-resins does not adversely affect the dry- or wet-shear strength of 2-ply Douglas-fir panels bonded with the modified resins. Reducing carbohydrates, however, cannot be used as the modifier. In general, addition of about 0.6–1.0 mole of modifier per mole of phenol is optimal in the formulation of carbohydrate-or polyol-modified resin. Preliminary results show that part but not all of the modifier is chemically bound into the resin, apparently through an ether linkage. The water prehydrolysate of southern red oak wood, when reduced with sodium borohydride to convert the reducing sugars to alditols, can be used to modify phenol-formaldehyde resins. This use of wood prehydrolysates can be economically beneficial to processes producing alcohol and chemicals from wood as well as to the wood industry and consumers of bonded wood products.     

Reactive compatibilization of a nitrile rubber/phenolic resin blend: Effect on adhesive and composite properties

Resole phenolic resins containing various p-cresol (PC) to phenol (P) mol ratios were prepared and characterized. These phenolic resins were blended with nitrile rubber (NBR) and the measurements of adhesive joint strength, stress–strain properties, DSC, TGA, DMA, TEM, and SEM were performed using a 50 : 50 NBR/phenolic resin blend. It was observed that the adhesive joint strength and the mechanical properties of the blend enhanced significantly on incorporation of p-cresol into the phenolic resin, and the optimum p-cresol/phenol mol ratio was in the vicinity of 2 : 1. Observation of a more continuous phase and the increase in T_g of the rubber region in the blend indicated increased reactivity and compatibilization of NBR with phenolic resin as p-cresol was incorporated. The effect of silica filler on the properties of the nitrile rubber/phenolic resin blend was also studied without and with p-cresol modification and the results suggest that silica filler take not only the role of a reinforcing filler in the nitrile–phenolic–silica composite, but also a role as surface compatibilizer of the blend components. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1187–1201, 1998     

Engineering Plastics from Lignin. IX. Phenolic Resin Synthesis and Characterization

The performance of phenol-formaldehyde (PF) resins, formulated with lignin derivatives previously synthesized as phenolic resin prepolymers, was evaluated by thermal analysis of the curing process, and by a hard maple shear block test. At 54 and 60% phenol replacement levels, respectively, kraft (KL) and steam explosion lignin (SEL)-based resoles exhibited cure behavior very similar to a standard PF resin. Acid hydrolysis lignin gelled prematurely, and was found to be incompatible with the normal synthesis procedure. Differential scanning calorimetry (DSC) was used to compare kinetic parameters for the curing process of neat and lignin derived phenolic resins. Activation energies and cure rates determined by DSC showed no difference between adhesives. High lignin contents had no inhibitory effect on resin cure. Shear strength properties were evaluated in a compression test, and results illustrate that both lignin-based resins have acceptable strength properties, both in a dry and accelerated aging test. Of the lignins tested, kraft lignin consistently demonstrated superior performance as a pre-polymer in phenolic adhesives. This was attributed to differences in the chemical structure of the two lignins, which had been found to vary in terms of their reactivity with formaldehyde and phenol. KL had been noted to be more amenable to derivatization with formaldehyde and phenol, hence its ability to crosslink with a phenol-formaldehyde fraction during resin synthesis was increased. Positive structural features in KL are a high phenolic guaiacyl (3-methoxy, 4-hydroxy phenyl) content, low carbon-to-carbon bonding between aromatic rings, high solubility in alkali, and a higher number average molecular weight than SEL.     

Studies on the adhesive properties of neoprene–phenolic blends

Polychloroprene (neoprene) rubber in combination with phenolic resins is a versatile adhesive formulation. The phenolic resin used in this case was derived from a mixture of cardanol, a meta-substituted naturally-occurring substance, and phenol. Cardanol is the main ingredient of cashew nut shell liquid (CNSL), a renewable resource. This study aims to investigate the adhesive properties of cardanol-based resin when used in combination with two grades of polychloroprene rubber. The effects of varying the solid content and resin content, choice of resin, fillers, crosslinking agents, adhesion promoters, solvents, etc. in the adhesive formulations were also studied. Moreover, relative proportions of rubber and resin that give optimum adhesion performance were identified. The results show that cardanol-phenol-formaldehyde resin is an effective ingredient in adhesives for bonding aluminium to aluminium and SBR to SBR. The addition of 3-aminopropyltriethoxysilane to the formulation improves the bond strength of metal-to-metal specimens.     

棉秆焦油替代苯酚合成酚醛树脂胶粘剂的研究

采用气/质联用仪(GC/MS)对棉秆焦油的成分进行了分析,确定了62种化合物,其中酚类化合物的相对含量为25.755%。用棉秆焦油部分替代苯酚合成酚醛树脂(PF)胶粘剂,并对其性能进行了研究。实验结果表明,棉秆焦油替代量对所合成的PF胶粘剂的粘度和胶合强度等性能影响较大;当m(棉秆焦油)=25g(即苯酚替代量达到19.2%)时,所制得的PF胶粘剂的粘度适中、w(游离甲醛)<0.5%,具有较高的胶合强度,并且胶合强度达到GB/T9846-2004标准中对Ⅰ类胶合板的要求。由于棉秆焦油的加入降低了PF胶粘剂的成本,因此,该PF胶粘剂具有良好的应用前景。     

Adhesive and thermal characteristics of maleimide-functional novolac resins

A novel, addition-curable maleimide-functional novolac phenolic resin was evaluated for adhesive properties such as lap shear strength and T-peel strength using aluminium adherends, when thermally self-cured and cocured with epoxy resins. The adhesive properties of the self-cured resin, although inferior at ambient temperature, improved at high temperature and were found to depend on the cure conditions. When cocured with epoxy resin, the adhesive properties improved significantly and showed a strong dependence on the nature of the epoxy resin used, on the stoichiometry of the reactants, on the concentration of imide groups in the phenolic resin, and on the extent of polymerization of the maleimide groups. Optimum adhesive properties were obtained for novolac resins with a moderate concentration of maleimide groups, taken on a 1 : 1 hydroxyl–epoxy stoichiometry with a novolac epoxy resin. In comparison to the conventional novolac, the imide–novolac contributed to improved adhesion and better adhesive property retention at higher temperature when cured with the novolac–epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 695–705, 1999     

Two‐component acrylic structural adhesive initiated by tributylborane for untreated PET adhesion

In order to improve the adhesion strength of acrylic adhesive to untreated poly(ethylene terephthalate) (PET) substrate, two‐component acrylic structural adhesives initiated by tributylborane were prepared. The effects of acrylic monomers, elastomers, decomplexers, and oligomers on the adhesion properties of two‐component acrylic structural adhesive were investigated in sequence. It is found that the shear strength on PET of adhesives toughened by acrylonitrile–butadiene–styrene copolymer and carboxyl‐terminated butadiene–acrylonitrile copolymer is higher than that of commercial adhesives Dp8010NS and Loctite 3030. A tailored oligomer was synthesized from hydroxyl propyl–terminated polydimethylsiloxane and 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate. It is also noticed that premature failure usually takes place in the lap shear test samples due to the brittleness of the acrylic adhesive, except in the sample of adhesive modified by tailored oligomer. Excellent adhesion to the PET substrate is achieved by this adhesive modified by tailored oligomer, with a lap shear strength above 11 MPa and T‐peel strength up to 5.34 N/mm. Additionally, the resulting adhesive is qualified for the structural bonding of PET materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46612.     

Thermoplastic and moisture-dependent behavior of lignin phenol formaldehyde resins

Bonding kinetics of thermosetting adhesives is influenced by a variety of factors such as temperature, humidity, and resin properties. A comparison of lignin-based phenol formaldehyde (LPF) and phenol formaldehyde (PF) adhesive in terms of reactivity and mechanical properties referring to testing conditions (temperature, moisture of specimen) were investigated. For this purpose, two resins were manufactured aiming for similar technological resin properties. The reactivity was evaluated by B-time measurements at different temperatures and the development of bonding strength at three different conditions, testing immediately after hot pressing, after applying a cooling phase after hot pressing, or sample conditioning at standard climate. In addition, the moisture stability of the two fully cured resins was examined. The calculated reactivity index demonstrated that LPF requires more energy for curing than PF. Further results indicate that lignin as substituent for phenol in PF resin has a negative impact on its moisture resistance. Additionally, the known thermoplastic behavior of lignin could also be detected in the behavior of the cured resin. This behavior is relevant for the adhesive in use and necessitates a cooling phase before testing the bonding strength development of lignin-based adhesive systems. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48011.     

The Effect of PEEK Fibres and Powder on Joints Made with a High Temperature Adhesive

High temperature adhesives typically exhibit low levels of peel strength since they tend to be more brittle than typical toughened adhesives used for lower temperature applications. It was found that incorporating thermoplastic fibres or powder into the bondline of a joint made with a high temperature epoxy-based adhesive resulted in significant improvements in peel strength. Poly(ether ether ketone) (PEEK) fibres and powder were incorporated into the adhesive resin and used in aluminium joints. These were tested in peel and single lap shear using a range of fibre lengths, orientations and volume fractions. It was seen that large increases in peel strength could be achieved but that lap shear strength was degraded with most types of modification. However, some modifications resulted in significant increases in peel strength with limited decrease in lap shear strength. These improved properties have been achieved using physical modifications rather than chemical alteration of the resin.     

Bond quality of soy-based phenolic adhesives in southern pine plywood

Increased demand for wood adhesives, environmental concerns, and the uncertainty of continuing availability of petrochemicals have led to recent attention on protein-based adhesives. This study was conducted to investigate the glue bond qualities of soy-based phenolic adhesive resins for southern pine plywood. Two types of soy-based resins were formulated and tested. The first was made by cross-linking soy flour with phenol-formaldehyde (pf) resins at neutral pH. The second type was obtained by cross-linking soy flour hydrolyzates with pf resin under alkaline conditions. Plywood bonded with the neutral phenolic soy resins containing 70% soy flour and 30% 1.6 g/cm² pf without the use of extenders and fillers compared favorably with the traditional southern pine pf glue mixes. Plywood bonded with alkaline phenolic soy resins, containing 40 or 50% 0.5 g/cm² PF with the addition of extender (19% corn-cob powder), provided better adhesive glue bond properties than traditional southern pine pf glue mixes. These results suggest that soy-based phenolic adhesive resins have potential for the production of exterior southern pine plywood.     

Design,Realization, and Characterization of Advanced Adhesives for Joining Ultra‐Stable C/C Based Components

The aim of this work is to develop high‐performance adhesives to join carbon fiber reinforced composites (C/C) for use in aerospace applications; in order to guarantee sound mechanical strength, a low coefficient of thermal expansion, and ease of application on large components. Several different adhesive formulations, based on phenolic or cyanate‐ester resins (charged with the maximum experimentally feasible amount of carbon‐based fillers), are developed and tested. The measurements of the lap shear strength at room temperature of the C/C joined by means of one phenolic and one cyanate ester‐based resin demonstrates that these formulations are the most suitable for the given application. A complete characterization, by means of viscosimetry, dilatometry, and thermal gravimetric analysis, coupled with gas analysis by means of mass spectroscopy, confirms that the phenolic‐based formulation is the most promising joining material. A nano‐indenter is used to obtain its Young modulus and hardness, both inside the joint and as a bulk cured adhesive.     

Durable adhesives for large laminated timber

Large laminated timber (LT) made of hardwood is widely used as the main constitutional element of goods such as furniture, pianos and doors. A high durability of LT is essential to these products. This study focused on finding as to what adhesives were acceptable as highly durable adhesives for LT. Twelve different adhesives such as resorcinol-formaldehyde resin, aqueous emulsion-type isocyanate resin, poly(vinyl acetate) emulsion, epoxy resin, etc. were used. The durability of LT, i.e., the percentage of delamination length of LT under tests such as humidity and temperature cycling tests, and outdoor tests, was discussed in relation to the adhesive shear strength of a lap joint (LJ). The results showed that the percentage of delamination length under both low ?20°C for 16 h and high-temperature 50°C for 8 h cycling tests (temperature-resistance) on LT indicated a strong trend with the adhesive shear strength of the LJ exposed to dry air at 100°C for 24 h. In addition, the percentage of delamination length under outdoor exposure test for three months (outdoor-resistance) of the LT showed a trend with the adhesive shear strength of the LJ exposed to dry air at 100°C for 24 h, as well as with the adhesive shear strength of the LJ immersed in water at 60°C for 3 h. These trends pointed out that the thermal stability of the adhesive from ?20°C for 16 h up to 50°C for 8 h was an important parameter in order to improve adhesive durability for the LT.     

Viscosity and Peel Strength of SMR 10-Based Pressure-Sensitive Adhesives

The viscosity and peel strength of a natural rubber-based pressure-sensitive adhesive was studied. One grade of natural rubber (SMR 10) and coumarone-indene resin were used as the elastomeric material and tackifier, respectively. Throughout the experiment, toluene was used as the solvent to prepare the adhesive. The effect of mastication time of rubber and tackifier concentration on the viscosity and peel strength of adhesive on various substrates was systematically investigated. The viscosity was measured using a HAAKE Rotary Viscometer. T-Test, 90° Adhesion To Steel (ATS), and 180° Adhesion To Steel (ATS) Tests were used to determine the peel strength of the adhesive. The results indicate that the viscosity of the adhesive increases with the resin content but decreases with mastication time. The peel strength generally increases with an increase in resin content except for the 20 min masticated sample. For all concentrations of the resin tackifier studied, the 10 min masticated sample exhibits the highest peel strength as compared to the corresponding values of the other masticated samples. This observation is attributed to the optimum wetting and formation of mechanical interlocking, and anchorage of the adhesive in pores and irregularities in the substrate for the former sample.     

Studies of Terminalia bellerica (Bahera), a natural gum,as an additive in a water-based adhesive composition

Terminalia bellerica (Bahera), a natural gum, was used as an additive in water-based natural rubber adhesive formulations. The lap shear strength of joints with wood substrates increased with the increase of natural gum concentration up to 80 phr (parts per hundred parts of rubber) loading. Similarly, the peel strength of the canvas to canvas joints increased with the incorporation of the gum. The results were explained with the help of viscoelastic properties, morphology and surface chemistry of the rubber–gum mixtures.     

Adhesive properties of blends of phenol/cardanol–formaldehyde copolymer resin with polychloroprene rubber

This is a continuation of an earlier study on the adhesive properties of neoprene–phenolic resin blends. The phenolic resin used is derived from a mixture of phenol and cardanol, a renewable resource. Having established the utility of cardanol for formulating adhesives, this study investigates the effect of varying the phenol: cardanol ratio in the formulation. The effect of varying the total resin content at various phenol/cardanol ratios is also studied. It is found that a phenol/cardanol ratio of 80:20 is optimum for shear strength of aluminum–aluminum bonds, while a 60:40 ratio is the best for peel properties. For SBR–SBR and SBR–Al bonds, a 60:40 ratio is optimum for both peel as well as shear strength. Further, an 80 phr total resin content in the primer and a 40 phr resin content in the adhesive are found to give the best shear and peel strengths for SBR–Al bonds. The study reveals that the copolymer based on phenol, cardanol and formaldehyde is a better choice for the resin than either of the individual condensation products of phenol or cardanol with formaldehyde.     

两步碱催化法制备尿素和三聚氰胺改性PF胶粘剂

采用两步碱催化法探讨了尿素(U)、三聚氰胺(M)和无机黏土等对酚醛树脂(PF)胶粘剂性能的影响.结果表明:适宜的n(甲醛):n(苯酚)比例是3.00:1或2.00:1;尿素改性可降低PF胶粘剂的生产成本,但其粘接强度减弱;三聚氰胺改性可提高PF胶粘剂的粘接强度,但其成本较高;无机黏土的加入可改善PMUF(苯酚-三聚氰胺...     

New epoxy-imide resins cured with bis(hydroxyphthalimide)s

New epoxy-imide resins were synthesized using bis(hydroxyphthalimide)s (BHPIs). Among these resins, that cured with BHPI(DDS), synthesized from 4,4′-diaminodiphenylsulfone, exhibits the best thermal resistance, reaching a tan δ maximum temperature of 230°C. This resin also features a tensile lap shear adhesive strength of 320 kgf/cm² when applied to steel test pieces. The cure reaction was followed by infrared spectroscopy and dynamic mechanical analysis. The ring-opening reaction between the phenolic hydroxyl group of BHPI and the epoxy group is observed, and accelerated by a tertiary amine catalyst, triethylamine.     

Effect of molecular structure of phenolic resin on solder dip resistance and peel strength of printed circuit adhesives

Phenolic resins were synthesized by using various kinds and amounts of catalyst and changing the mole ration of formaldehyde and phenol. The solder dip resistance and the peel strength were measured for two-component printed circuit adhesives mixed with poly(vinyl acetal) resin, and the relation between these properties and the molecular structure of the phenolic resins were studied. Catalysts such as ammonia, amines having low boiling points, and alkaline earth metal oxide and hydroxides give resins with good properties. When the mole ratios of ammonia to phenol and formaldehyde to phenol are respectively 0.05–0.10 and 1.5, the resins obtained have good characteristics. The solder dip resistance is improved by aging the resin solution at moderate temperature.