Polyethylene terephthalate

Polyethylene terephthalate (aka. PET, PETE, PETP) is a thermoplastic resin of the polyester family that is used to make beverage, food and other liquid containers, synthetic fibers, as well as for some other thermoforming applications. It is also one of the most important raw materials used in man-made fibers. Depending on its processing and thermal history, it may exist both as an amorphous (transparent) and as a semi-crystalline (opaque and white) material. It can be synthesized by a transesterification reaction between ethylene glycol and dimethyl terephthalate. It is manufactured under trade names Arnite, Impet and Rynite, Hostaphan, Melinex and Mylar films, and Dacron, Terylene & Trevira fibers. [1]

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Uses

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The main virtue of PET is that it is fully recyclable. Unlike other plastics, its polymer chains can be recovered for additional use. PET has a resin identification code of 1.

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PET can be semi-rigid to rigid, depending on its thickness, and is very lightweight. It makes a good gas and fair moisture barrier, as well as a good barrier to alcohol (requires additional "Barrier" treatment) and solvents. It is strong and impact-resistant. It is naturally colorless and transparent.

When produced as a thin film (often known by the tradename Mylar), PET is often coated with aluminium to reduce its permeability, and to make it reflective and opaque. PET bottles are excellent barrier materials and are widely used for soft drinks, (see carbonation). For certain specialty bottles, PET sandwiches an additional polyvinyl alcohol to further reduce its oxygen permeability.

When filled with glass particles or fibers, it becomes significantly stiffer and more durable. This glass-filled plastic, in a semi-crystalline formulation, is sold under the tradename Rynite.

PET was patented in 1941 by the Calico Printer's Association of Manchester. The PET bottle was patented in 1973. Alpek is a major producer of PET in Mexico.

Intrinsic viscosity

One of the most important characteristics of PET is referred to as I.V.(intrinsic viscosity) The I.V. of the material, measured in dl/g (deciliters/gram) is dependent upon the length of its polymer chains. The longer the chains, the stiffer the material, and therefore the higher the I.V. The average chain length of a particular batch of resin can be controlled during polymerization.

An I.V. of about:

0.60 - Would be appropriate for fiber

0.65 - Film

0.76-0.84 - Bottles

0.85 - Tire cord

Drying

PET is hygroscopic, meaning that it naturally absorbs water from its surroundings. However when this 'damp' PET is then heated a chemical reaction known as hydrolysis takes place between the water and the PET which reduces its molecular weight (IV) and its physical properties. This means that before the resin can be processed in a molding machine, as much moisture as possible must be removed from the resin. This is achieved through the use of a dessicant.

Inside the dryer, hot dry air is pumped into the bottom of the hopper containing the resin so that it flows up through the pellets removing moisture on its way. The hot wet air leaves the top of the hopper and is first run through an after-cooler, because it is easier to remove moisture from cold air than hot air. The resulting cool wet air is then passed through a desiccant bed. Finally the cool dry air leaving the desiccant bed is re-heated in a process heater and sent back through the same processes in a closed loop. Typically residual moisture levels in the resin must be less than 40 ppm before processing. Dryer residence time should not be shorter than about four hours. This is because drying the material in less than 4 hours would require a temperature above 160 °C, at which level hydrolysis would begin inside the pellets before they could be dried out.

Copolymers

In addition to pure (homopolymer) PET, PET modified by copolymerization is also available.

In some cases, the modified properties of copolymer are more desirable for a particular application. For example, cyclohexane dimethanol (CHDM) can be added to the polymer backbone in place of ethylene glycol. Since this building block is much larger (6 additional carbon atoms) than the ethylene glycol unit it replaces, it does not fit in with the neighboring chains the way an ethylene glycol unit would. This interferes with crystallization and lowers the polymer's melting temperature.

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Another common modifier is isophthalic acid, replacing some of the 1,4- (para-) linked terephthalate units. The 1,2- (ortho-) or 1,3- (meta-) linkage produces an angle in the chain, which also disturbs crystallinity.

Such copolymers are advantageous for certain molding applications, such as thermoforming, which is used to make tray or blister packages from PET sheet (sometimes called APET, for "amorphous PET"). On the other hand, crystallization is important in other applications where mechanical and dimensional stability are important, such as seat belts. For PET bottles, the use of small amounts of CHDM or other comonomers can be useful: if only small amounts of comonomers are used, crystallization is slowed but not prevented entirely. As a result, bottles are obtainable via stretch blow molding ("SBM"), which are both clear and crystalline enough to be an adequate barrier to aromas and even gasses, such as the carbon dioxide in carbonated beverages.

Crystals

Crystallization occurs when polymer chains fold up on themselves in a repeating, symmetrical pattern. Long polymer chains tend to become entangled on themselves, which prevents full crystallization in all but the most carefully controlled circumstances. PET is no exception to this rule; 60% crystallization is the upper limit for commercial products, with the exception of polyester fibers.

PET in its natural state is a crystalline resin. Clear products can be produced by rapidly cooling molten polymer to form an amorphous solid. Like glass, amorphous PET forms when its molecules are not given enough time to arrange themselves in an orderly fashion as the melt is cooled. At room temperature the molecules are frozen in place, but if enough heat energy is put back into them, they begin to move again, allowing crystals to nucleate and grow.

Like most materials, PET tends to produce many small crystallites when crystallized from an amorphous solid, rather than forming one large single crystal. Light tends to scatter as it crosses the boundaries between crystallites and the amorphous regions between them. This scattering means that crystalline PET is opaque and white in most cases. Fiber drawing is among the few industrial processes that produces a nearly single-crystal product.

Degradation

When PET degrades, several things happen, mainly the formation of acetaldehyde and cross-links ("gel" or "fish-eye" formation). Acetaldehyde is normally a colorless gas with a fruity smell. It forms naturally in fruit, but it can cause an off-taste in bottled water. Acetaldehyde forms in PET through the "abuse" of the material. High temperatures (PET decomposes above 300 °C or 572 °F), high pressures, extruder speeds (excessive shear flow raises temperature) and long barrel residence times all contribute to the production of acetaldehyde. When acetaldehyde is produced, some of it remains dissolved in the walls of a container and then diffuses into the product stored inside, altering the taste and aroma. This is not such a problem for non-consumables such as shampoo, for fruit juices, which already contain acetaldehyde or for strong-tasting drinks, such as soft drinks. For bottled water, low acetaldehyde content is quite important, because if nothing masks the aroma, even extremely low concentrations (10-20 ppb) of acetaldehyde can produce an off-taste.

One way to alleviate this is to use a copolymer. Comonomers such as CHDM or isophthalic acid lower the melting temperature of PET. Thus the resin can be plastically formed at lower temperatures and/or with lower force. This helps to prevent degradation, reducing the acetaldehyde content of the finished product to an acceptable (that is, unnoticeable) level. See copolymers, above.

Antimony

Antimony trioxide (Sb₂O₃) is a catalyst that is often used in the production of PET. It remains in the material and can migrate out into food and drinks. The Swiss Federal Office of Public Health compared the amount of antimony in waters bottled in PET and glass: the antimony concentrations of the water in PET bottles was somewhat higher, but still well below the allowed maximal concentrations.[2] (report available in German and French only) The Swiss Federal Office of Public Health concluded that the health risk of these low concentrations is negligible (1% of the "tolerable daily intake" determined by the WHO) — although antimony is very toxic at much higher concentrations . A later (2006) study by a group of geochemists [3] finds similar concentrations of antimony in water bottled in PET and, comparing it with concentrations in groundwater and in natural water bottled both in polypropylene and glass, concludes that Sb is leaching from PET; however, it does not discuss health risks for humans. The most recent WHO risk assessment for antimony in drinking water can be found here: [4]

Re-crystallization

PET can be used to explore the crystallization of amorphous solids. The resin identification code can be used to verify the type of plastic is made of: many plastic beverage bottles have the letters PET or PETE and a code of 1 on the bottom, near the center. When a flame is held several inches below the bottle and slowly brought closer, part of the material will visibly change. This happens because high temperatures melt the PET. This releases the tension that was frozen in during the blow molding process and the polymer chains will shift to a more relaxed and disordered state, which results in shrinkage of the softened area. Because of the decreased order of the polymer chains, there are now fewer crystal nuclei. Consequently, when the crystallites re-form upon cooling they grow larger than the original crystallites in the bottle wall. Because the new crystallites are larger than the wave length of light, they will now cause light to scatter, giving the material an opaque white appearance.

Processing Equipment

There are two basic molding methods, one-step and two-step. In two-step molding, two separate machines are used, one for injection molding the perform, the second for stretch-blow molding it into the final container shape. In one-step machines, the entire process from raw material to finished container is conducted within one machine, making it especially suitable for molding non-standard shapes (custom molding), including jars, flat oval, flask shapes etc. Its greatest merit is the reduction in space, product handling and energy, and far higher visual quality than can be achieved by the two-step system.

See also

• Recycling of PET Bottlesde:Polyethylenterephthalat