Polymers environmental stress cracking

Besides the stress of state in the polymer, environmental stress cracking in polymers involves both solubility and absorption rate phenomena. Sensitizing media that cause ESC can be divided into two categories those that swell or wet the polymer and those that chemically react with the polymer. The medium may be gaseous or liquid. The former mechanism has been the subject of numerous studies and is commonly recognized as the primary cause of the majority of chemically induced failures of polymers. Although both amorphous and semicrystalline polymers are susceptible to ESC, it is well known that amorphous polymers tend to be more at risk. The close packing of chains in the crystalline domains of semicrystalline polymers acts as a barrier to fluid. 

Resistance to Chemical Environments and Solubility. As a rule, amorphous plastics are susceptible, to various degrees, to cracking by certain chemical environments when the plastic material is placed under stress. The phenomenon is referred to as environmental stress cracking (ESC) and the resistance of the polymer to failure by this mode is known as environmental stress cracking resistance (ESCR). The tendency of a polymer to undergo ESC depends on several factors, the most important of which are appHed stress, temperature, and the concentration of the aggressive species. 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

In the case of crystalline polymers it may be that solvents can cause cracking by activity in the amorphous zone. Examples of this are benzene and toluene with polyethylene. In polyethylene, however, the greater problem is that known as environmental stress cracking , which occurs with materials such as soap, alcohols, surfactants and silicone oils. Many of these are highly polar materials which cause no swelling but are simply absorbed either into or on to the polymer. This appears to weaken the surface and allows cracks to propagate from minute flaws. 

It is well known that LCB has a pronounced effect on the flow behavior of polymers under shear and extensional flow. Increasing LCB will increase elasticity and the shear rate sensitivity of the melt viscosity ( ). Environmental stress cracking and low-temperature brittleness can be strongly influenced by the LCB. Thus, the ability to measure long chain branching and its molecular weight distribution is critical in order to tailor product performance. 

Mechanical properties of plastics can be determined by short, single-point quality control tests and longer, generally multipoint or multiple condition procedures that relate to fundamental polymer properties. Single-point tests include tensile, compressive, flexural, shear, and impact properties of plastics creep, heat aging, creep rupture, and environmental stress-cracking tests usually result in multipoint curves or tables for comparison of the original response to post-exposure response. 

The remainder of this section on environmental decay of polymers is devoted to the physical interaction between polymer and environment. This is what in general is called "environmental stress cracking", which thus is only one part of the story. 

In environmental stress cracking the material fails by breaking when exposed to mechanical stress in the presence of organic liquids or wetting agents (soap solutions, etc.). A well-known example is the action of carbon tetrachloride in polycarbonate a little drop of this liquid on a strip of this polymer causes a very fast cracking upon a little bending of the strip. 

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