Mechanisms of criticality in environmental adhesion loss.

Moisture attack on adhesive joints is a long-standing scientific and engineering problem. A particularly interesting observation is that when the moisture level in certain systems exceeds a critical concentration, the bonded joint shows a dramatic loss of strength. The joint interface plays a dominant role in this phenomenon; however, why a critical concentration of moisture exists and what role is played by the properties of the bulk adhesive have not been adequately addressed. Moreover if the interface is crucial, the local water content near the interface will help elucidate the mechanisms of criticality more than the more commonly examined bulk water concentration in the adhesive. To gain a detailed picture of this criticality, we have combined a fracture mechanics approach to determine joint strength with neutron reflectivity, which provides the moisture distribution near the interface. A well-defined model system, silica glass substrates bonded to a series of polymers based on poly(n-alkyl methacrylate), was utilized to probe the role of the adhesive in a systematic manner. By altering the alkyl chain length, the molecular structure of the polymer can be systematically changed to vary the chemical and physical properties of the adhesive over a relatively wide range. Our findings suggest that the loss of adhesion is dependent on a combination of the build-up of the local water concentration near the interface, interfacial swelling stresses resulting from water absorption, and water-induced weakening of the interfacial bonds. This complexity explains the source of criticality in environmental adhesion failure and could enable design of adhesives to minimize environmental failure.

On the origins of sudden adhesion loss at a critical relative humidity: examination of bulk and interfacial contributions.

The origins for abrupt adhesion loss at a critical relative humidity (RH) for polymeric adhesives bonded to inorganic surfaces have been explored using a model poly(methyl methacrylate) (PMMA) film on glass. The interfacial and bulk water concentrations within the polymer film as a function of D 2O partial pressure were quantified using neutron reflectivity. Adhesion strength of these PMMA/SiO 2 interfaces under the same conditions was quantified using a shaft loaded blister test. A drop in adhesion strength was observed at a critical RH, and at this same RH, a discontinuity in the bulk moisture concentration occurred. The moisture concentration near the interface was higher than that in the bulk PMMA, and at the critical RH, the breadth of the interfacial water concentration distribution as a function of distance from the SiO 2/PMMA interface increased dramatically. We propose a mechanism for loss of adhesion at a critical RH based upon the interplay between bulk swelling induced stress and weakening of the interfacial bond by moisture accumulation at the PMMA/SiO 2 interface.