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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. According to ASTM D883, stress cracking is defined as "an external or internal crack in a plastic caused by tensile stresses less than its short-term mechanical strength". This type of cracking typically involves brittle cracking, with little or no ductile drawing of the material from its adjacent failure surfaces. Environmental stress cracking may account for around 15-30% of all plastic component failures in service. This behavior is especially prevalent in glassy, amorphous thermoplastics. Amorphous polymers exhibit ESC because of their loose structure which makes it easier for the fluid to permeate into the polymer. Amorphous polymers are more prone to ESC at temperature higher than their glass transition temperature (Tg) due to the increased free volume. When Tg is approached, more fluid can permeate into the polymer chains.
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. These corrosive environmental liquids are called 'secondary chemical agents', are often organic, and are defined as solvents not anticipated to come into contact with the plastic during its lifetime of use. Failure is rarely associated with primary chemical agents, as these materials are anticipated to come into contact with the polymer during its lifetime, and thus compatibility is ensured prior to use. In air, failure due to creep is known as creep rupture, as the air acts as a plasticizer, and this acts in parallel to environmental stress cracking.
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. Environmental stress cracking is accelerated due to higher temperatures, cyclic loading, increased stress concentrations, and fatigue.
Metallurgists typically use the term Stress corrosion cracking or Environmental stress fracture to describe this type of failure in metals.
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.
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. ESC may occur continuously, or a piece-wise start and stop mechanism
There is an array of experimentally derived evidence to support the above theories:
ESC generally occurs at the surface of a plastic and doesn't require the secondary chemical agent to penetrate the material significantly, which leaves the bulk properties unmodified.
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Environmental stress cracking AI simulator
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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. According to ASTM D883, stress cracking is defined as "an external or internal crack in a plastic caused by tensile stresses less than its short-term mechanical strength". This type of cracking typically involves brittle cracking, with little or no ductile drawing of the material from its adjacent failure surfaces. Environmental stress cracking may account for around 15-30% of all plastic component failures in service. This behavior is especially prevalent in glassy, amorphous thermoplastics. Amorphous polymers exhibit ESC because of their loose structure which makes it easier for the fluid to permeate into the polymer. Amorphous polymers are more prone to ESC at temperature higher than their glass transition temperature (Tg) due to the increased free volume. When Tg is approached, more fluid can permeate into the polymer chains.
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. These corrosive environmental liquids are called 'secondary chemical agents', are often organic, and are defined as solvents not anticipated to come into contact with the plastic during its lifetime of use. Failure is rarely associated with primary chemical agents, as these materials are anticipated to come into contact with the polymer during its lifetime, and thus compatibility is ensured prior to use. In air, failure due to creep is known as creep rupture, as the air acts as a plasticizer, and this acts in parallel to environmental stress cracking.
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. Environmental stress cracking is accelerated due to higher temperatures, cyclic loading, increased stress concentrations, and fatigue.
Metallurgists typically use the term Stress corrosion cracking or Environmental stress fracture to describe this type of failure in metals.
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.
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. ESC may occur continuously, or a piece-wise start and stop mechanism
There is an array of experimentally derived evidence to support the above theories:
ESC generally occurs at the surface of a plastic and doesn't require the secondary chemical agent to penetrate the material significantly, which leaves the bulk properties unmodified.