Environmental stress cracking
Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic (especially amorphous) polymers known at present. Environmental stress cracking may account for around 15-30% of all plastic component failures in service.
ESC and polymer resistance to ESC (ESCR) have been studied for several decades. Research shows that the exposure of polymers to liquid chemicals tends to accelerate the crazing process, initiating crazes at stresses that are much lower than the stress causing crazing in air. The action of either a tensile stress or a corrosive liquid alone would not be enough to cause failure, but in ESC the initiation and growth of a crack is caused by the combined action of the stress and a corrosive environmental liquid.
It is somewhat different from polymer degradation in that stress cracking does not break polymer bonds. Instead, it breaks the secondary linkages between polymers. These are broken when the mechanical stresses cause minute cracks in the polymer and they propagate rapidly under the harsh environmental conditions. It has also been seen that catastrophic failure under stress can occur due to the attack of a reagent that would not attack the polymer in an unstressed state.
Although the phenomenon of ESC has been known for a number of decades, research has not yet enabled prediction of this type of failure for all environments and for every type of polymer. Some scenarios are well known, documented or are able to be predicted, but there is no complete reference for all combinations of stress, polymer and environment. The rate of ESC is dependent on many factors including the polymer’s chemical makeup, bonding, crystallinity, surface roughness, molecular weight and residual stress. It also depends on the liquid reagent's chemical nature and concentration, the temperature of the system and the strain rate.
Mechanisms of ESC
There are a number of opinions on how certain reagents act on polymers under stress. Because ESC is often seen in amorphous polymers rather than in semicrystalline polymers, theories regarding the mechanism of ESC often revolve around liquid interactions with the amorphous regions of polymers. One such theory is that the liquid can diffuse into the polymer, causing swelling which increases the polymer’s chain mobility. The result is a decrease in the yield stress and glass transition temperature (Tg), as well as a plasticisation of the material which leads to crazing at lower stresses and strains. A second view is that the liquid can reduce the energy required to create new surfaces in the polymer by wetting the polymer’s surface and hence aid the formation of voids, which is thought to be very important in the early stages of craze formation.
There is an array of experimentally derived evidence to support the above theories:
- Once a craze is formed in a polymer this creates an easy diffusion path so that the environmental attack can continue and the crazing process can accelerate.
- Chemical compatibility between the environment and the polymer govern the amount in which the environment can swell and plasticise the polymer.
- The effects of ESC are reduced when crack growth rate is high. This is primarily due to the inability of the liquid to keep up with the growth of the crack.
A number of different methods are used to evaluate a polymer’s resistance to environmental stress cracking. A common method in the polymer industry is use of the Bergen jig, which subjects the sample to variable strain during a single test. The results of this test indicate the critical strain to cracking, using only one sample. Another widely used test is the Bell Telephone test where bent strips are exposed to fluids of interest under controlled conditions. Current research deals with the application of fracture mechanics to the study of ESC phenomena.
An obvious example of the need to resist ESC in everyday life is the automotive industry, in which a number of different polymers are subjected to a number of fluids. Some of the chemicals involved in these interactions include petrol, brake fluid and windscreen cleaning solution. Plasticisers leaching from PVC can also cause ESC over an extended period of time, for example. One of the first examples of the problem concerned ESC of LDPE. The material was initially used in insulating electric cables, and cracking occurred due to the interaction of the insulation with oils. The solution to the problem lay in increasing the molecular weight of the polymer. A test of exposure to a strong detergent such as Igepal was developed to give a warning of ESC.
SAN piano key
A more specific example comes in the form of a piano key made from injection moulded styrene acrylonitrile (SAN). The key has a hook end which connects it to a metal spring, which causes the key to spring back into position after being struck. During assembly of the piano an adhesive was used, and excess adhesive which had spilled onto areas where it was not required was removed using a ketone solvent. Some vapour from this solvent condensed on the internal surface of the piano keys. Some time after this cleaning, fracture occurred at the junction where the hook end meets the spring.
To determine the cause of the fracture, the SAN piano key was heated above its glass transition temperature for a short time. If there is residual stress within the polymer, the piece will shrink when held at such a temperature. Results showed that there was significant shrinkage, particularly at the hook end-spring junction. This indicates stress concentration, possibly the combination of residual stress from forming and the action of the spring. It was concluded that although there was residual stress, the fracture was due to a combination of the tensile stress from the spring action and the presence of the ketone solvent.
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