Epoxy adhesives temperature resistance

Additives to improve heat and/or moisture resistance are also known for epoxy adhesives. In a unique metal-ceramic bonding application, 100-150 mesh glass powder has been used to impart heat (arc) resistance to epoxy adhesives.Heat resistance is improved when the glass melts (>448°C), flows, and adheres to the two substrates. Uretidinedione compounds, e.g., l,3-bis(3-isocyanato-4-methylphenyl)-2,4-uretidinedione (83), have been used in room temperature curing compositions to impart excellent heat and moisture resistance. Adhesive strength was not found to be affected even after heating in steam at 120°C and 2 atm. 

Polysulfides and stability, and compatibility with epoxies high temperature resistance RT rapid cure times Poor performance at Consumer adhesives ... 

The corrosion resistance and polymer-bonding compatibilities of the lonizable organophosphonates and the neutral organo-silanes are directly related to their inherent chemical properties. Specifically, NTMP inhibits the hydration of AI2O2 and maintains or Improves bond durability with a nitrile-modified epoxy adhesive which is cured at an elevated temperature. The mercaptopropyl silane, in addition to these properties, is compatible with a room temperature-cured epoxy-polyamide primer and also exhibits resistance to localized environmental corrosion. These results, in conjunction with the adsorbed Inhibitor films and the metal substrate surfaces, are subsequently discussed. 

As shown in Table 15.5, the epoxy plastics have fair resistance to high temperatures and have good mechanical properties. Cured epoxy resins are resistant to nonoxidizing acids, alkalis, and salts. Because of the presence of polar hydroxyl pendant groups, these polymers have good adhesion to substrates such as wood or metal. 

Structural adhesives are formulated from epoxy resins, phenolic resins, acrylic monomers and resins, high temperature-resistant resins (e.g., polyimidcs), and urethanes. Structural adhesive resins arc often modified by elastomers. 

Pyromellitic dianhydride (PMDA) is a solid having a melting point of 286°C. It contains two anhydride groups symmetrically attached to a benzene ring. Because of the compactness of the molecule, PMDA achieves very high crosslink densities and, therefore, high heat and chemical resistance. PMDA cured epoxy adhesives have a heat distortion temperature on the order of 280 to 290°C. 

Benzyldimethylamine (BDMA) is another tertiary amine that can be used as either a sole catalyst or an accelerator with other curing agents. It is used with DGEBA epoxy resins at 6 to 10 pph. The pot life is generally 1 to 4 h, and the cure will be complete in about 6 days at room temperature. When used by itself, BDMA can provide epoxy adhesive formulations with high-temperature resistance (Chap. 15). However, BDMA is mostly used as an accelerator for anhydride and dicyandiamide cured epoxy resins. 

Hybrid resins have been used to improve the flexibility, thermal shock resistance, elongation, heat distortion temperature, and impact strength of unmodified epoxy adhesives. However, there can also be some sacrifice in certain physical properties due to the characteristics of the additive. These alloys result in a balance of properties, and they almost never result in the combination of only the beneficial properties from each component without carrying along some of their downside. 

Epoxy-nitrile Nitrile-epoxy adhesives are composed of solid epoxy resin modified with carboxyl-terminated butadiene nitrile (CTBN) copolymer. The CBTN is introduced into die epoxy resin at elevated temperatures. The modification provides toughness and high peel strength without sacrificing heat and chemical resistance. The film adhesives are widely used in the aerospace industry in the construction of jetliners. 

Polysulfide resins combine with epoxy resins to provide adhesives and sealants with excellent flexibility and chemical resistance. These adhesives bond well to many different substrates. Tensile shear strength and elevated-temperature properties are low. However, resistance to peel forces and low temperatures is very good. Epoxy polysulfides have good adhesive properties down to -100°C, and they stay flexible to -65°C. The maximum service temperature is about 50 to 85°C depending on the epoxy concentration in the formulation. Temperature resistance increases with the epoxy content of the system. Resistance to solvents, oil and grease, and exterior weathering and aging is superior to that of most thermoplastic elastomers. 

Functionalized, liquid polybutadiene derivatives have also been developed as hybrid flexiblizers for epoxy resins. Carboxyl-terminated butadiene/acrylonitrile polymers, butadiene homopolymers, and maleic anhydride-amino acid grafted butadiene homopolymers have been used as flexibilizers to impart good low-temperature strength and water resistance to DGEBA-based epoxy adhesives. An epoxy system toughened by polybutadiene with maleic anhydride is claimed to provide a hydrophobic backbone, low viscosity, softness, and high tensile strength and adhesion (Table 7.10). 

Talc or hydrated magnesium silicate is another mineral that is used to reinforce epoxy adhesives. It has a platelike structure that provides good stiffness and creep resistance at elevated temperatures. It also provides good electrical and chemical resistance characteristics.26 It is relatively inexpensive and disperses well in the resin. 

Aluminum powder, in particular, is frequently employed at relatively high concentrations in high-temperature epoxy adhesive formulations. The filler provides improvement in both tensile strength and heat resistance, and it increases the thermal conductivity of the adhesive. Aluminum powder fillers also reduce undercut corrosion and, hence, improve adhesion and durability of epoxy adhesive between bare steel substrates. It is believed that this is accomplished by the aluminum filler providing a sacrificial electrochemical mechanism.27... 

The most significant differences in performance properties between a two-component, room temperature curing epoxy adhesive and a one-component, heat-curing type are the heat and chemical resistance. These differences are due primarily to the lower crosslink density or glass transition temperature of the room temperature curing types. 

Chemical resistance is similarly affected by curing agent type and the temperature of the cure. Moisture, solvent, and general chemical resistance are usually superior for epoxy adhesives that are cured at elevated temperatures. Room temperature epoxy adhesives, having a lower glass transition temperature, are more severely affected by environmental exposures. 

Table 11.8 presents a typical triethylenetetramine cured epoxy adhesive formulated with selected fillers. In this formulation the use of aluminum powder and alumina increases substantially the resistance of the adhesive to boiling water.7 This is also true when DETA is used as the curing agent.8 A typical room temperature cured aliphatic amine cured epoxy adhesive for general-purpose use is shown in Table 11.9. This shows the difference that is achieved in shear strength by curing at elevated temperatures versus room temperature.

The room temperature cured epoxy adhesives discussed thus far exhibit a general lack of flexibility, especially when considered next to elastomeric sealants. Flexibility is generally desired when the performance requirements include high peel strength, impact strength, and resistance to thermal shock or thermal cycling. 

There are several ways by which the formulator can moderately improve the heat or chemical resistance of room temperature curing epoxy adhesives. Using an elevated-temperature cure or a postcure will, of course, improve the temperature resistance by virtue of improved crosslink density. However, this section describes formulations that have been developed for moderately improved heat resistance after only a cure at room temperature. Optimal (heat-curing) high-temperature and chemically resistant epoxy adhesives are discussed in Chap. 15. 

Temperature-resistant two-part, elevated-temperature curing epoxy adhesives can be formulated with aromatic amines, such as metaphenylenediamine (MPDA), methylene dianiline (MDA), or a eutectic blend of the two. These adhesives will provide relatively high temperature strength, but they are generally brittle. When mixed with epoxy resin at concentrations of about 15 pph for MPDA and 26 pph for MDA, they provide complete cure in about 30 min at 175°C. The aromatic amines also provide a working life of several hours at room temperature. Starting formulations for aromatic amine cured epoxy adhesives are shown in Table 12.4. 

Several formulations of elevated-temperature curing epoxy adhesives have been developed with improved thermal resistance and greater toughness. The next section describes the processes and materials that can be used to achieve moderately better heat resistance and toughness. However, formulations with the optimum temperature resistance are discussed in Chap. 15, and tougheners are described in Chap. 8. 

Benzoquinone tetracarboxylic acid dianhydride (BTDA) has been found to provide epoxy adhesives with excellent high-temperature properties, in both the short and long terms. The formulation described in Table 12.12 provides good resistance to 260°C. This two-part adhesive can be cured 2 h at 200°C. The disadvantage of BTDA is that relatively high cure temperatures are required that result in a high degree of internal stress within the bond line. 

However, newer adhesives systems having moderate temperature resistance have been developed with improved toughness but without sacrificing other properties. When cured, these structural adhesives have discrete elastomeric particles embedded in the matrix. The most common toughened hybrids using this concept are acrylic and epoxy systems. The elastomer is generally a amine- or carboxyl-terminated acrylonitrile butadiene copolymer (ATBN and CTBN). 

However, waterborne epoxy systems are not without certain disadvantages, which have limited their application as adhesives. These disadvantages include increased use of energy to evaporate the water and dry the adhesive, lower resistance of the cured film to high-humidity environments, and storage and application limitations due to potential freezing at low temperatures. 

Strength and permanence are influenced by many common environmental elements. These include high and low temperatures, moisture or relative humidity, chemical fluids, and outdoor weathering. Table 15.1 summarizes the relative resistance of various types of epoxy adhesives to common operating environments. 

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