Amorphous and crystalline polymers

The spaghetti-like entanglements of polymer molecules tend to produce amorphous solids, but it often happens that some parts can become sufficiently aligned to produce a region exhibiting crystal-like order, so it is not uncommon for some polymeric solids to consist of a random mixture of amorphous and crystalline regions. As might be expected, shorter and less-branched polymer chains can more easily organize themselves into ordered layers than have can long chains. Hydrogen-bonding between adjacent chains also helps, and is very important in fiber-forming polymers both synthetic (Nylon 6.6) and natural (cotton cellulose).

Pure crystalline solids have definite melting points, but polymers, if they melt at all, exhibit a more complex behavior. At low temperatures, the tangled polymer chains tend to behave as rigid glasses. For example, the natural polymer that we call rubber becomes hard and brittle when cooled to liquid nitrogen temperature. Many synthetic polymers remain in this state to well above room temperature.

In some polymers (known as thermoplastics) there is a fairly definite softening point that is observed when the thermal kinetic energy becomes high enough to allow internal rotation to occur within the bonds and to allow the individual molecules to slide independently of their neighbors, thus rendering them more flexible and deformable. This defines the glass transition temperature t_g .

Depending on the degree of crystallinity, there will be a higher temperature, the melting point t_m , at which the crystalline regions come apart and the material becomes a viscous liquid. Such liquids can easily be injected into molds to manufacture objects of various shapes, or extruded into sheets or fibers. Other polymers (generally those that are highly cross-linked) do not melt at all; these are known as thermosets. If they are to be made into molded objects, the polymerization reaction must take place within the molds — a far more complicated process. About 20% of the commercially-produced polymers are thermosets; the remainder are thermoplastics.