Epoxies degradation resistance

Sihcones (qv) have an advantage over organic resias ia their superior thermal stabiUty and low dielectric constants. Polyurethanes, when cured, are tough and possess outstanding abrasion and thermal shock resistance. They also have favorable electrical properties and good adhesion to most surfaces. However, polyurethanes are extremely sensitive to and can degrade after prolonged contact with moisture as a result, they are not as commonly used as epoxies and sihcones (see Urethane polymers). 

This task represents a continuation of efforts to maximize the hydrophobicity of acrylic, epoxy, and other polymeric systems for resistance to water penetration and environmental degradation, and to minimize the dielectric constant and improve the processability for adhesives and coatings, without compromising the necessary structural characteristics for materials used for, e.g., structural elements, liners, paints, and microelectronic devices. 

For many years prior to the development of high-temperature thermoplastics and thermosets, such as the polyimides. polysulfones, and epoxies, phenolic molding material dominated the high temperature-resistant market. This emphasizes their ability to resist temperature degradation in the 400-500°F (204-260 C) range. Because phenolics were found to possess excellent ablative properties, it has been reported that both the American and Soviet space efforts used them in combination with certain other... 

Epoxy resins and curing agents must have a relatively low viscosity so that formulation compounding can be accomplished easily and without a great deal of energy or degradation of the components. Viscosity is defined as the resistance of a liquid material to flow. It is usually measured in fundamental units of poise (P) or centipoise (cP). Table 3.2 shows a relationship between various common fluids and their viscosity as measured in centipoise. 

Diluents will also affect the performance properties of the adhesive. Diluents generally lower the degree of crosslinking and degrade the physical properties of the cured epoxy. This reduction in crosslink density increases the resiliency of the adhesive, but it also reduces tensile strength as well as heat and chemical resistance. These effects are more pronounced at elevated temperatures than at room temperature. The degree of these effects will depend on whether the diluent has epoxy functionality (reactive diluents) or whether the diluent is incapable of reacting with the epoxy system (nonreactive diluents). 

Monofunctional epoxy diluents are used primarily with DGEBA epoxy blends. The most common monofunctional diluents are butyl glycidyl ether and phenyl glycidyl ether. The effect of butyl glycidyl ether and other reactive diluents on the viscosity of epoxy resin is shown in Fig. 6.3. Because the monofunctional diluents reduce crosslink density, they are used at relatively low levels to avoid degrading heat and chemical resistance or other properties of the adhesive. 

However, the single-phase epoxy nitrile adhesive achieves its high peel strength by bulk elongation. Other properties, such as heat and chemical resistance, are generally degraded as they are when other flexibilizers or plasticizers are added to the epoxy. The two-phase version of this adhesive hybrid solves many of these problems. 

Epoxy-nylon adhesives are limited to a maximum service temperature of 85°C, and they exhibit poor creep resistance. Possibly their most serious limitation is poor moisture resistance because of the hydrophilic nylon (polyamide) constituent.9 The degradation by exposure to moisture occurs with both the cured and uncured adhesives. 

Nonconductive fillers are employed with electrical-grade epoxy adhesive formulations to provide assembled components with specific electrical properties. Metallic fillers generally degrade electrical resistance values, although they could be used to provide a degree of conductivity as discussed above. 

The effect of electrical-grade fillers (e.g., silica) on the electrical properties of the adhesive is usually marginal. Generally fillers are not used to improve electrical resistance characteristics such as dielectric strength. The unfilled epoxy is usually optimal as an insulator. Also under conditions of high humidity, fillers may tend to wick moisture and considerably degrade the electrical resistance properties of the adhesive. 

The above analysis applies to degradation processes that relate to the bulk adhesive. Interfacial degradation processes such as corrosion can be similarly determined. Thermal and oxidative stability, as well as corrosion and water resistance, depends on the adherend surface as well as on the adhesive itself. Epoxy-based adhesives degrade less rapidly at elevated temperatures when in contact with glass or aluminum than when in contact with copper, nickel, magnesium, or zinc. The divalent metals have a more basic oxide surface than the higher-valence metal oxides and hence serve to promote dehydrogenation reactions, which lead to anion formation and chain scission.7... 

Certain adhesive systems are more resistant to interfacial degradation by moist environments than are other adhesives. Table 15.16 illustrates that a nitrile-phenolic adhesive does not succumb to failure through the mechanism of preferential displacement at the interface. Failures occurred cohesively within the adhesive even when tested after 24 months of immersion in water. A nylon-epoxy adhesive bond, however, degraded rapidly under the same conditioning owing to its permeability and preferential displacement by moisture. 

Plasticizer migration from the vinyl part into the adhesive bond line can degrade the strength of the joint. Adhesives must be tested for their ability to resist the plasticizer. PVC can be made with a variety of plasticizers. An adhesive suitable for a certain flexible PVC formulation may not be compatible with a PVC from another supplier. Nitrile rubber adhesives have been found to be very resistant to plasticizers and are often the preferred adhesive for flexible PVC films. However, certain epoxy adhesive formulations have also been found to provide excellent adhesion to flexible PVC substrates. Several such starting formulations are presented in Table 16.7. A comparison of the performance of several classes of adhesive when bonding PVC to itself and to various other materials is given in Table 16.15. 

Noise resistance monitoring has been used to track the long-term degradation of marine coatings under laboratory exposures (153), and remotely under natural exposure conditions (154). In studies of epoxy and alkyd coatings on steel... 

The high moisture absorption of aramid fibers is their biggest disadvantage. It was reported in the literature that moisture absorption by epoxy laminates degrades their mechanical properties. ° ° Hygroscopic fibers provide an easy route for moisture ingress. The addition of aramid fibers to epoxy and phenolic composites slightly improves their flame resistance and decreases smoke formation. ... 

Salt-spray data (for nos. 1 and 2 in Table V) indicated that, on zinc-phosphated steel, cathodic ED indeed led to considerably better corrosion resistance. On bare steel, however, both cathodic and anodic coatings failed completely. Further, we prepared a number of different, amine-modified epoxy resin esters containing between 30 and 50 %w of drying fatty acids (e.g. no. 3 in Table V). These could all be deposited cathodically and again attained excellent salt-spray ratings on phosphated steel but performed poorly on bare steel. We concluded that cathodic ED prevents phosphate layer degradation (a well-known phenomenon with anodic ED) and thus leads to superior corrosion resistance on pretreated steel. On bare steel the binders performed too poorly to allow comparison between cathodic and anodic ED. 

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