Epoxy–imide resins from N‐(4‐ and 3‐carboxyphenyl)trimellitimides. I. Adhesive and thermal properties

Epoxy–imide resins were obtained by curing Araldite GY 250 (diglycidyl ether of bisphenol‐A and epichlorohydrin; difunctional) and Araldite EPN 1138 (Novolac–epoxy resin; polyfunctional) with N‐(4‐ and 3‐carboxyphenyl)trimellitimides derived from 4‐ and 3‐aminobenzoic acids and trimellitic anhydride. The adhesive lap shear strength of epoxy–imide systems at room temperature and at 100, 125, and 150°C was determined on stainless‐steel substrates. Araldite GY 250‐based systems give a room‐temperature adhesive lap shear strength of about 23 MPa and 49–56% of the room‐temperature adhesive strength is retained at 150°C. Araldite EPN 1138‐based systems give a room‐temperature adhesive lap shear strength of 16–19 MPa and 100% retention of room‐temperature adhesive strength is observed at 150°C. Glass transition temperatures of the Araldite GY 250‐based systems are in the range of 132–139°C and those of the Araldite EPN 1138‐based systems are in the range of 158–170°C. All these systems are thermally stable up to 360°C. The char residues of Araldite GY 250‐ and Araldite EPN 1138‐based systems are in the range of 22–26% and 41–42% at 900°C, respectively. Araldite EPN 1138‐based systems show a higher retention of adhesive strength at 150°C and have higher thermal stability and T_g when compared to Araldite GY 250‐based systems. This has been attributed to the high crosslinking possible with Araldite EPN 1138‐based systems arising due to the polyfunctional nature of Araldite EPN 1138. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1729–1736, 2000     

Chemical phosphorylation improves the moisture resistance of soy flour‐based wood adhesive

A green‐chemistry approach to improve the moisture resistance of soy flour (SF)‐based wood adhesive is described. Chemical phosphorylation of SF (PSF), using POCl₃ as the phosphorylating agent, dramatically increased its wet bond strength. The optimum POCl₃:SF ratio that produced maximum wet bond strength was about 0.15 (g g^?1). The increase in wet bond strength of PSF (PSF0.15) was mostly due to the phosphate groups incorporated into the proteins and carbohydrates, and to a lesser degree to phosphorylation‐induced protein denaturation. The attached phosphate groups acted as cross‐linking agents, either via covalent esterification with hydroxyl groups on wood chips or via ionic and hydrogen‐bonding interactions with functional groups in wood chips. At hot‐press temperatures above 160°C the wet bond strength of PSF0.15 was >2.6 MPa, a level that might be acceptable for interior‐used hardwood plywood and particleboard. POCl₃ is a low cost, general‐purpose reagent and therefore PSF‐based adhesive is expected to be environmentally friendly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40451.     

Bond strength of hybrid sol–gel coatings with different additives

The hybrid sol–gel coating on Al 2024-T3 was modified by adding polyaniline, TiO₂, or γ-Al₂O₃ nanoparticles in the formulation separately. The coating was then used as an adhesive to bond Al 2024-T3 alloys, forming a single lap joint. The bond strength of the sol–gel coating was investigated using a universal tensile test machine. The lap shear strength of the original sol–gel coating was about 1.38 MPa and it was increased up to 2.26 MPa after the modification by adding 0.05 wt% PANI microparticles in the sol–gel coating. The small increase in strength was attributed to an improvement in its adhesive flexibility because of incorporation of the long-chain organic polymer in its structure. Furthermore, the addition of different amounts of TiO₂ nanoparticles in the unmodified sol–gel coating also led to an increase in shear strength compared to the undoped sol–gel coating. Typically, a sol–gel coating containing 2.0 wt% of TiO₂ recorded the highest adhesive strength of about 4.0 MPa. A similar increase in strength was observed when doping γ-Al₂O₃ nanoparticles into the original hybrid sol–gel coating. Adding 0.5 wt% of γ-Al₂O₃ in the sol–gel coating increased the adhesive bonding strength up to 4.48 MPa. The fracture surface of the specimen was separately observed by SEM and Optical Microscopy in order to examine potential evidences of mechanism and nature of failure. The reason why the adhesive strength increased after the modification of the sol–gel coating is discussed in this article.     

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.     

Heterocyclic‐based epoxy‐terminated structural adhesive. II. Curing,adhesive strength,and thermal stability

We studied the curing behavior of heterocyclic‐based epoxy‐terminated resins using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylicdianhydride, and the commercial hardener of Ciba‐Geigy's two‐pack Araldite as curing agents. The adhesive strength of the adhesives was measured by various ASTM methods such as lap‐shear, peel, and cohesive tests on metal–metal, wood–wood, and wood–metal interfaces. All of these results were compared with those of an epoxy resin prepared from bisphenol‐A and epichlorohydrin resin with an epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3520–3526, 2002     

Novel whey protein‐based aqueous polymer‐isocyanate adhesive for glulam

Whey, a by‐product of cheese making, contains whey proteins, lactose, vitamins, and minerals. Whey and whey proteins are still not fully used. In this study, whey protein‐based aqueous polymer‐isocyanate (API) adhesives were developed and characterized by bond test, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscope (SEM) for bond strength, chemical structures, and morphology. The optimized whey protein‐based API adhesive for Glulam had a 28‐h boiling‐dry‐boiling wet strength of 6.81 MPa and a dry strength of 14.34 MPa. Results indicated that the addition of polyvinyl acetate emulsion can prolong the work life of the API adhesive. Addition of crosslinker polymeric methylene bisphenyl diisocyanate (P‐MDI) not only increased the cohesive strength of the cured adhesive by crosslinking whey proteins but also resulted in strong chemical bonds via urethane linkage in wood bondlines. Addition of polyvinyl alcohol (PVA) further increased the crosslinking density of the cured adhesive due to its capability of crosslinking whey proteins through the reaction with P‐MDI. Nanoscale CaCO₃ powder (3.5 wt %) as filler significantly improved bond strength due to its mechanical interlock with the polymers in the adhesive. SEM examinations confirmed that both PVA and nanoscale CaCO₃ improved the compatibilities of the components in the optimized whey protein‐based API adhesive. FTIR results revealed that P‐MDI reacts mainly with the residual amino groups rather than the hydroxyl groups of whey proteins. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Epoxy-based composite adhesives with improved lap shear strengths at high temperatures for steel-steel bonded joints

High-performance room temperature-cure epoxy structural adhesives utilizing simplified formulation are developed. The developed structural adhesive consists of diglycidyl ether of bisphenol A (DGEBA) and novolac epoxy blend as a base resin, micrometer-sized silica particles as a reinforcing filler, and triethylenetetramine as a curing agent. The developed ambient temperature-cure epoxy structural adhesive with optimized formulation exhibits outstanding properties including high glass transition temperature of 95°C, high thermal stability with degradation temperature at 5% weight loss of 364°C, exceptionally high rubbery plateau modulus of 320 MPa, good flame-retardant characteristics with limiting oxygen index of 40, and high single lap shear strength for single lap steel-steel bonded joint of 548 MPa at the temperature of 80°C. The silica-filled DGEBA/novolac epoxy composite adhesive is a potential candidate for applying as a structural adhesive for construction with long-term durability.     

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     

Bio-adhesion evaluation of a chitosan-based bone bio-adhesive

Conventional treatment of complex fractures includes the use of plates and nails, which may compromise the affected limb's functionality. Previous studies have demonstrated promising results through chemical, mechanical, and cytotoxicity tests of a chitosan-based adhesive—proposed as a new method to bond high energy fractures—in dry environments with adequate adhesion, malleability, and biocompatibility. In this study, we focused on performing an evaluation of bio-adhesives’ mechanical properties and bone-adhesive joint using two chitosan-based formulations (with and without a cross-linking agent). The texture profile analysis determined adhesive properties, such as cohesiveness, adhesiveness, hardness, and resilience at different cure times. Bone-adhesive joint was evaluated according to the tensile bond strength test and shear bond strength test. Fracture toughness and cohesive strength were calculated through a rigid double cantilever beam test at mode I failure. Bone-adhesive joints were tested in two environments: dry and submersed in water at 37 °C for 1, 6, and 24 h (curing time), an approximation of surgery conditions. The experimental results showed an incremental of adhesiveness and hardness of the cross-linked adhesive during the first 15 min, which was determined as the usage time to spread on the bone fracture. The joint interaction between the adhesive and bone surfaces was studied; chitosan-based formulations showed an adhesive joint failure under dry conditions in most of the cases. However, this behavior changed under aqueous conditions, presenting cohesive failures. Under aqueous conditions, cross-linked bone-adhesive presented an augmented tensile bond strength up to 0.024 ± 0.0036 MPa, a shear bond strength up to 0.031 ± 0.0069 MPa, and fracture toughness of 2.38 ± 0.54 J/m² was observed with a cure time of 24 h. Finally, the presence of the cross-linking agent in the cross-linked bio-adhesive reduced the sensitivity of the adhesive to water; a promising finding that should be explored in future studies.     

The Impacts of Heat Treatment on Lap Joint Shear Strength of Black Pine Wood

This study was conducted to determine the impacts of heat treatment on lap shear strength, density, and mass loss of black pine wood. In the study, black pine wood boards bonded with polyurethane were subjected to temperatures of 160, 180, and 200°C for durations of 2 and 6 hours. Specimens having two layers were prepared from untreated and treated wood for mechanical testing of bond lines. Data were analyzed using variance analysis and Tukey's test to determine the impacts of changes in density and mass of heat-treated black pine wood on lap shear strength. The results indicated that the lap shear strength of black pine wood decreased as the intensity of heat treatment increased. The results also indicated that the minimum and maximum percentage decreases of lap shear strength were approximately 27% for 160°C and 2 hours and 78% for 200°C and 6 hours.     

Comparison of fracture behavior between acrylic and epoxy adhesives

An experimental study was conducted on the strength of adhesively bonded steel joints, prepared epoxy and acrylic adhesives. At first, to obtain strength characteristics of these adhesives under uniform stress distributions in the adhesive layer, tensile tests for butt, scarf and torsional test for butt joints with thin-wall tube were conducted. Based on the above strength data, the fracture envelope in the normal stress-shear stress plane for the acrylic adhesive was compared with that for the epoxy adhesive. Furthermore, for the epoxy and acrylic adhesives, the effect of stress triaxiality parameter on the failure stress was also investigated. From those comparison, it was found that the effect of stress tri-axiality in the adhesive layer on the joint strength with the epoxy adhesive differed from that with the acrylic adhesive. Fracture toughness tests were then conducted under mode l loading using double cantilever beam (DCB) specimens with the epoxy and acrylic adhesives. The results of the fracture toughness tests revealed continuous crack propagation for the acrylic adhesive, whereas stick-slip type propagation for the epoxy one. Finally, lap shear tests were conducted using lap joints bonded by the epoxy and acrylic adhesives with several lap lengths. The results of the lap shear tests indicated that the shear strength with the epoxy adhesive rapidly decreases with increasing lap length, whereas the shear strength with the acrylic adhesive decreases gently with increasing the lap length.     

Formulation of a novel soybean protein‐based wood adhesive with desired water resistance and technological applicability

A novel soybean protein‐based wood adhesive with good bond strength, excellent water resistance, and the desired technological applicability was formulated by combining thermal alkali degradation, thermal acid treatment, and crosslinking. The characterization results indicated that thermal alkali degradation could effectively improve the technological applicability, thermal acid treatment could positively improve the water resistance, and appropriate crosslinking modification could significantly enhance the bond strength and water resistance of the soybean protein adhesive. The crosslinker species, crosslinker level, and ratio of thermal alkali‐degraded soybean protein (DSP) to thermal acid‐treated soybean protein (TSP) had important effects on the primary properties of the soybean protein adhesives. The modified polyamide aqueous solution was the most preferable crosslinker because of its low viscosity, good crosslinking efficiency, and excellent miscibility with soybean protein solution. The optimal soybean protein adhesive that was formulated from 20 wt % modified polyamide as the crosslinker and a DSP/TSP ratio of 1:3 had a solid content of more than 35 wt %, suitable viscosity (～2180 mPa s), a long work life (>16 h), good dry bond strength (2.94 MPa), and 28 h of boiling–dry–boiling cycled wet strength (1.29 MPa) that met the required values for structural use according to JIS K6806‐2003 commercial standards. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43586.     

Influence of chemical structure of hardener on mechanical and adhesive properties of epoxy polymers

The mechanical and adhesive properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact and uniaxial compression tests were used to determine the impact energy, elastic modulus and yield stress, respectively. The adhesion tests were carried out in steel–steel joints using single‐lap shear, T‐peel, and impact adhesive joints geometry. The better mechanical and adhesive behavior of the networks is obtained when exists high flexibility of chain between crosslink and/or high elastic modulus. The 1‐(2‐aminoethyl)piperazine epoxy network presents the best adhesive properties, high flexibility, and the largest impact energy. However, it possesses low elastic modulus and yield stress. Also, exhibits increases in peel strength and impact energy while reductions in lap shear strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of chitosan‐based adhesives and assessment of their mechanical properties

The aim of this study is to develop chitosan‐based adhesives and to characterize their shear strength. The desirable features of such adhesives are biodegradability, biocompatibility, non‐toxicity, and anti‐microbial properties. Various eco‐friendly polyanionic polysaccharides, acids, and plasticizers, in single or multiple formulations, were associated with chitosan. The resulting crosslinked polymers were glued on some chemically treated aluminum adherends. The shear strength of these formulations was measured with the “double lap‐joint” bonding method, as it features a low‐peeling effect. The shear strength of 40.8 MPa obtained for formulations containing chitosan and glycerol plasticizer was the most significant finding in this study. This value is equivalent to that obtained with a synthetic adhesive used in industry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A Formaldehyde-Free Water-Resistant Soy Flour-Based Adhesive for Plywood

The phasing out of the use of urea–formaldehyde adhesive in the fabrication of interior‐used hardwood plywood requires development of environmentally friendly bio‐based wood adhesives. We recently reported that phosphorylation of soy flour (SF) using phosphoryl chloride (POCl₃) greatly improved the moisture resistance of soy flour adhesive. In the present study, we investigated the effects of inorganic oxidizing agents, such as NaClO₂ and Ca(NO₂)₂, to further improve the wet bonding strength of phosphorylated SF (PSF) wood adhesive. We report that addition of 1.8 % (wet weight basis) Ca(NO₂)₂ to phosphorylated SF (PSF) adhesive formulation containing 25 % soy flour solids increased the wet bonding strength to greater than 3 MPa at 140 °C hot‐press temperature. The water resistance testing of the glued three‐ply hardwood plywood panels passed the three‐cycle soak/dry test recommended by the American National Standard for Hardwood and Decorative Plywood/Hardwood Plywood and Veneer Association protocol (ANSI/HPVA HP‐1‐2004). Since the process involves only inorganic chemistry and no petroleum‐based chemicals such as formaldehyde or polyamidoamine–epichlorohydrin are used, the PSF + Ca(NO₂)₂ adhesive is non‐toxic and environmentally safe.     

Effect of hydrolysis and denaturation of wheat gluten on adhesive bond strength of wood joints

In this study the adhesive bond strength of different wheat gluten modifications and the relationship between molecular weight and adhesive strength was examined. Guanidine hydrochloride and sodium hydroxide were used as denaturation and dispersing agent. Additionally wheat proteins were hydrolyzed by alkaline conditions and enzymes. Effects of different treatments were observed by viscosity measurements and gel electrophoresis. Wood lap joints were prepared with modified proteins and tensile shear strength was tested under dry and wet conditions. In situ hardening of different formulations was analyzed by means of DMA with two‐layered specimens in a three‐point bending test set‐up. Higher solubility had no positive effect on dry bonding strength and wet bonding strength was even reduced. Depending on the degree of hydrolysis, significant improvement of adhesive bond strength was observed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrolyte‐resistant epoxy for bonding batteries based on sandwich structures

Adhesives that are stable in Li‐ion battery electrolytes are required to realize the potential of new battery designs that integrate structural elements with energy storage. Here, several polymers, commercial adhesives, and sealants were investigated to bond and seal a Li‐ion battery sandwich panel. Gravimetric electrolyte uptake measurements were compared with Hansen solubility parameters to predict long‐term durability of the materials exposed to battery electrolyte. The durability of adhesively bonded joints with an epoxy adhesive, which was selected as the lowest electrolyte uptake material, was examined using single lap shear strength tests and three‐point bending tests in a fabricated sandwich panel. The strength of the epoxy decreased after exposure to battery electrolyte due to solvent uptake in the bond. The addition of lithium hexafluorophosphate to the ethylene carbonate/dimethyl carbonate mixture severely decreased the strength with respect to the pure solvents. In device testing, the sandwich panel did not show any visible damage or leakage when loaded to above 1000 N during three‐point bending tests. Using sol extraction measurements and differential scanning calorimetry analyses, the optimized curing temperature for the epoxy adhesive ranged from 80 to 100 °C. At these temperatures, the cured adhesive had a highly crosslinked structure with low sol extraction. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46059.     

Process optimization of solvent based polybenzimidazole adhesive for aerospace applications

The use of adhesive bonding for high temperature applications is becoming more challenging because of low thermal and mechanical properties of commercially available adhesives. However, the development of high performance polymers can overcome the problem of using adhesive bonding at high temperature. Polybenzimidazole (PBI) is one such recently emerged high performance polymer with excellent thermal and mechanical properties. It has a tensile strength of 160 MPa and a glass transition of 425 °C. Currently, PBI is available in solution form with only 26% concentration in Dimethyl-acetamide solvent. Due to high solvent contents, the process optimization required lot of efforts to form PBI adhesive bonded joints with considerable lap shear strength. Therefore, in present work, efforts are devoted to optimize the adhesive bonding process of PBI in order to make its application possible as an adhesive for high temperature applications. Bonding process was optimized using different curing time and temperatures. Epoxy based carbon fiber composite bonded joints were successfully formed with single lap shear strength of 21 Mpa. PBI adhesive bonded joints were also formed after performing the atmospheric pressure plasma treatment of composite substrate. Plasma treatment has further improved the lap shear strength of bonded joints from 21 MPa to 30 MPa. Atmospheric pressure plasma treatment has also changed the mode of failure of composite bonded joints.     

Improved adhesive properties and bonding performance of HTPB‐based polyurethane elastomer by using aziridine‐type bond promoter

Theeffect of two aziridine‐type bond promoters on adhesive and mechanical properties of a hydroxyl terminated polybutadiene‐based elastomeric liner used in solid propellant rockets was investigated by varying the concentration to determine the optimum value. The performance of butyleneiminetrimesoylaziridine (BITA) was compared with that of tris[1‐2‐methylaziridinyl]phosphine oxide (MAPO) in the elastomeric liner of otherwise the same composition. The adhesive performance of the elastomer to the composite was determined by using metal‐elastomer‐composite tensile and peel tests. The adhesive performance of the elastomer to the metal was also determined, this time by using peel and shear tests. The mechanical characterization of the elastomer was done by tensile and hardness tests. A significant enhancement in the bonding performance of the elastomeric liner toward composite propellant and metal case was achieved by optimizing the concentration of bond promoter in the elastomeric composition. All the elastomer compositions with bond promoters BITA and MAPO loadings of 1.0, 1.5, and 2.0 wt % were found to be sufficient for the rocket motor operations because the interfacial adhesive strength of these compositions is higher than the cohesive strength of the composite. Compositions with bond promoter quantities of 1.0, 1.5, 2.0, and 2.5 wt % have better strength values than the others. Liner compositions with the bond promoter BITA give better bonding performance between the composite–metal system and better mechanical properties when compared with the elastomers with the bond promoter MAPO. The best results are obtained in terms of bonding performance and adhesive properties by using the bond promoter BITA in optimized quantities of 1.0 and 1.5 wt % loadings in the elastomer compositions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 806–814, 2001     

Synthesis and properties of fluorene‐based polyimide adhesives

Five kinds of fluorene‐based polyimides (PIs) based on 4,4′‐oxydiphthalicanhydride (ODPA), 9,9′‐bis(4‐aminophenyl)fluorene (BAFL), and 3,4′‐diaminodiphenyl ether (3,4′‐ODA) were synthesized through two‐step method. The partially or fully imidized PI films were cast from poly(amic acid) (PAA) solution and were imidized by far‐infrared radiation at various temperatures. The degree of imidization was characterized by FT‐IR and TGA. The fully imidized PI films were characterized by DMTA, TGA, and tensile tests. The partially imidized PI films were adhered to stainless steel plates for preparing the single lap joints. Lap shear strength (LSS) at room temperature was measured to compare the adhesive strength of single lap joint. Fractured surfaces were analyzed using scanning electron microscopy (SEM). The effects of fluorene content on thermal, tensile, and adhesion properties of PIs were elaborately studied. The results showed that PI films exhibited high glass transition temperature (T_g), good thermalplasticity, and thermal stability. The LSS of PIs increased abruptly with the incorporation of fluorene groups. The LSS of PI‐50/50 was the highest, which was 22.3 MPa. The LSS of PI‐50/50 was also measured at high temperature to investigate the thermal resistance of fluorene‐based PI adhesive. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.