PET Jars and Bottles

Polyethylene terephthalate (sometimes written poly(ethylene terephthalate)), commonly abbreviated PET, PETE, or the obsolete PETP or PET-P, is a thermoplastic polymer resin of the polyester family and is used in synthetic fibers; beverage, food and other liquid containers; thermoforming applications; and engineering resins often in combination with glass fiber.

Depending on its processing and thermal history, polyethylene terephthalate may exist both as an amorphous (transparent) and as a semi-crystalline polymer. The semicrystalline material might appear transparent (particle size < 500 nm) or opaque and white (particle size up to a few microns) depending on its crystal structure and particle size. Its monomer (bis-β-hydroxyterephthalate) can be synthesized by the esterification reaction between terephthalic acid and ethylene glycol with water as a byproduct, or by transesterification reaction between ethylene glycol and dimethyl terephthalate with methanol as a byproduct. Polymerization is through a polycondensation reaction of the monomers (done immediately after esterification/transesterification) with ethylene glycol as the byproduct (the ethylene glycol is directly recycled in production).

The majority of the world's PET production is for synthetic fibers (in excess of 60%) with bottle production accounting for around 30% of global demand. In discussing textile applications, PET is generally referred to as simply "polyester" while "PET" is used most often to refer to packaging applications. The polyester industry makes up about 18% of world polymer production and is third after polyethylene (PE) and polypropylene (PP).

Uses

Sailcloth is typically made from PET fibers also known as polyester or under the brand name Dacron; colorful lightweight spinnakers are usually made of nylon.

PET can be semi-rigid to rigid, depending on its thickness, and it 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 with a high transparency.

Plastic bottles made from PET 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.

Biaxially oriented PET film (often known by one of its trade names, "Mylar") can be aluminized by evaporating a thin film of metal onto it to reduce its permeability, and to make it reflective and opaque (MPET). These properties are useful in many applications, including flexible food packaging and thermal insulation, such as "space blankets". Because of its high mechanical strength, PET film is often used in tape applications, such as the carrier for magnetic tape or backing for pressure sensitive adhesive tapes.

Non-oriented PET sheet can be thermoformed to make packaging trays and blisters. If crystallizable PET is used, the trays can be used for frozen dinners, since they withstand both freezing and oven baking temperatures.

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, Arnite, Hostadur, and Crastin.


While most thermoplastics can, in principle, be recycled, PET bottle recycling is more practical than many other plastic applications. The primary reason is that plastic carbonated soft drink bottles and water bottles are almost exclusively PET. PET has a resin identification code of 1. One of the uses for a recycled PET bottle is for the manufacture of polar fleece material. Among its many uses, companies such as English Retreads use the PET material to line their products. It can also make fiber for polyester products.

Because of the recyclability of PET and the relative abundance of post-consumer waste in the form of bottles, PET is rapidly gaining market share as a carpet fiber. Mohawk Industries released everSTRAND in 1999, a 100% post-consumer recycled content PET fiber. Since that time, more than 17 billion bottles have been recycled into carpet fiber.[4] Pharr Yarns, a supplier to numerous carpet manufacturers including Looptex, Dobbs Mills, and Berkshire Flooring,produces a BCF (bulk continuous filament) PET carpet fiber containing a minimum of 25% post-consumer recycled content.

PET, as with many plastics, is also an excellent candidate for thermal disposal (incineration), as it is composed of carbon, hydrogen, and oxygen, with only trace amounts of catalyst elements (but no sulfur). PET has the energy content of soft coal.

PET was patented in 1941 by the Calico Printers' Association of Manchester. The PET bottle was patented in 1973 by Nathaniel Wyeth.

One of the most important characteristics of PET is referred to as intrinsic viscosity (IV)

The intrinsic viscosity of the material, measured in deciliters per gram (dℓ/g) is dependent upon the length of its polymer chains. The longer the polymer chains, the more entanglements between chains and therefore the higher the viscosity. The average chain length of a particular batch of resin can be controlled during polycondensation.

The intrinsic viscosity range of PET

Fiber grade
0.40 – 0.70 dℓ/g Textile
0.72 – 0.98 dℓ/g Technical, tire cord

Film grade
0.60 – 0.70 dℓ/g BoPET (biaxially oriented PET film)
0.70 – 1.00 dℓ/g Sheet grade for thermoforming

Bottle grade
0.70 – 0.78 dℓ/g Water bottles (flat)
0.78 – 0.85 dℓ/g Carbonated soft drink grade

Monofilament
1.00 – 2.00 dℓ/g
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Drying

PET is hygroscopic, meaning that it naturally absorbs water from its surroundings. However, when this 'damp' PET is then heated, the water hydrolyzes the PET, decreasing its resilience. 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 desiccant or dryers before the PET is fed into the processing equipment.

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 5 parts per million (parts of water per million parts of resin, by weight) 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.

PET can also be dried in compressed air resin dryers. Compressed air dryers do not reuse drying air. Dry, heated compressed air is circulated through the PET pellets as in the desiccant dryer, then released to the atmosphere.
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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. Such PET is generally known as PETG (Eastman Chemical and SK Chemicals are the only two manufacturers). PETG is a clear amorphous thermoplastic that can be injection molded or sheet extruded. It can be colored during processing.

Replacing terephthalic acid (right) with isophthalic acid (center) creates a kink in the PET chain, interfering with crystallization and lowering the polymer's melting point.

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 for example to make tray or blister packaging from PETG film, or PETG sheet. 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 gases, such as carbon dioxide in carbonated beverages.

Crystallization of polymers 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. This procedure is known as solid-state crystallization.

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 produce a nearly single-crystal product.

PET is subject to various types of degradations during processing. The main degradations that can occur are hydrolytic, thermal and, probably most important, thermal oxidation. When PET degrades, several things happen: discoloration, chain scissions resulting in reduced molecular weight, formation of acetaldehyde and cross-links ("gel" or "fish-eye" formation). Discoloration is due to the formation of various chromophoric systems following prolonged thermal treatment at elevated temperatures. This becomes a problem when the optical requirements of the polymer are very high, such as in packaging applications. The thermal and thermooxidative degradation results in poor processibility characteristics and performance of the material.

One way to alleviate this is to use a copolymer. Comonomers such as CHDM or isophthalic acid lower the melting temperature and reduce the degree of crystallinity of PET (especially important when the material is used for bottle manufacturing). 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. Other ways to improve the stability of the polymer is by using stabilizers, mainly antioxidants such as phosphites. Recently, molecular level stabilization of the material using nanostructured chemicals has also been considered.

Acetaldehyde is normally a colorless, volatile substance 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 570 °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 like soft drinks. For bottled water, however, low acetaldehyde content is quite important, because if nothing masks the aroma, even extremely low concentrations (10–20 parts per billion in the water) of acetaldehyde can produce an off-taste.

Antimony (Sb) is a catalyst that is often used as antimony trioxide (Sb2O3) or antimony triacetate in the production of PET. After manufacturing a detectable amount of antimony can be found on the surface of the product. This residue can be removed with washing. Antimony also remains in the material itself and can thus migrate out into food and drinks. Exposing PET to boiling or microwaving can increase the levels of antimony significantly, possibly above USEPA maximum contamination levels.[9] The drinking water limit in the USA for antimony is 6 parts per billion.[10] Although antimony trioxide is of low toxicity when taken orally,[11] its presence is still of concern. The Swiss Federal Office of Public Health investigated the amount of antimony migration, comparing waters bottled in PET and glass: the antimony concentrations of the water in PET bottles were higher, but still well below the allowed maximum concentration. The Swiss Federal Office of Public Health concluded that small amounts of antimony migrate from the PET into bottled water, but that the health risk of the resulting low concentrations is negligible (1% of the "tolerable daily intake" determined by the WHO). A later (2006) but more widely publicized study found similar amounts of antimony in water in PET bottles.[12] The WHO has published a risk assessment for antimony in drinking water.[11]

Possible toxicity of PET

Commentary published in Environmental Health Perspectives in April 2010 suggested that PET might yield endocrine disruptors under conditions of common use and recommended[13] research on this topic. Proposed mechanisms include leaching of phthalates as well as leaching of antimony. Other authors (FRANZ and WELLE) published evidence based on mathematical modeling, indicating that it is quite unlikely that PET yields endocrine disruptors in mineral water.[14]

Bottle processing equipment

There are two basic molding methods for PET bottles, one-step and two-step. In two-step molding, two separate machines are used. The first machine injection molds the preform, which resembles a test tube, with the bottle-cap threads already molded into place. The body of the tube is significantly thicker, as it will be inflated into its final shape in the second step using stretch blow molding.

In the second process, the preforms are heated rapidly and then inflated against a two-part mold to form them into the final shape of the bottle. Preforms (uninflated bottles) are now also used as containers for candy, and by some Red Cross chapters to distribute to homeowners to store medical history for emergency responders.[15]

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.

Polyester recycling industry

When recycling polyethylene terephthalate or PET or polyester, two ways generally have to be differentiated:

The chemical recycling back to the initial raw materials purified terephthalic acid (PTA) or dimethyl terephthalate (DMT) and ethylene glycol (EG) where the polymer structure is destroyed completely, or in process intermediates like bis-ß-hydroxyterephthalate
The mechanical recycling where the original polymer properties are being maintained or reconstituted.

Chemical recycling of PET will become cost-efficient only applying high capacity recycling lines of more than 50,000 tons/year. Such lines could only be seen, if at all, within the production sites of very large polyester producers. Several attempts of industrial magnitude to establish such chemical recycling plants have been made in the past but without resounding success. Even the promising chemical recycling in Japan has not become an industrial break through so far. The two reasons for this are: at first, the difficulty of consistent and continuous waste bottles sourcing in such a huge amount at one single site, and, at second, the steadily increased prices and price volatility of collected bottles. The prices of baled bottles increased for instance between the years 2000 and 2008 from about 50 Euro/ton to over 500 Euro/ton in 2008.

Mechanical recycling or direct circulation of PET in the polymeric state is operated in most diverse variants today. These kinds of processes are typical of small and medium-sized industry. Cost-efficiency can already be achieved with plant capacities within a range of 5 000 – 20 000 tons/year. In this case, nearly all kinds of recycled-material feedback into the material circulation are possible today. These diverse recycling processes are being discussed hereafter in detail.

Besides chemical contaminants and degradation products generated during first processing and usage, mechanical impurities are representing the main part of quality depreciating impurities in the recycling stream. Recycled materials are increasingly introduced into manufacturing processes, which were originally designed for new materials only. Therefore, efficient sorting, separation and cleaning processes become most important for high quality recycled polyester.

When talking about polyester recycling industry, we are concentrating mainly on recycling of PET bottles which are meanwhile used for all kinds of liquid packaging like water, carbonated soft drinks, juices, beer, sauces, detergents, household chemicals and so on. Bottles are easy to distinguish because of shape and consistency and separate from waste plastic streams either by automatic or hand sorting processes. The established polyester recycling industry consists of three major sections:
PET bottle collection and waste separation—waste logistics
Production of clean bottle flakes—flake production
Conversion of PET flakes to final products—flake processing

Intermediate product from the first section is baled bottle waste with a PET content greater than 90%. Most common trading form is the bale but also bricked or even loose, pre-cut bottles are common in the market. In the second section the collected bottles are converted to clean PET bottle flakes. This step can be more or less complex and complicated depending on required final flake quality. During third step PET bottle flakes are processed to any kind of products like film, bottles, fiber, filament, strapping or intermediates like pellets for further processing and engineering plastics.

Besides this external (post-consumer) polyester bottle recycling, numbers of internal (pre-consumer) recycling processes exist, where the wasted polymer material does not exit the production site to the free market, and instead is reused in the same production circuit. In this way, fiber waste is directly reused to produce fiber, preform waste is directly reused to produce preforms, and film waste is directly reused to produce film.
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PET bottle recycling

see article: PET bottle recycling
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Purification and decontamination

The success of any recycling concept is hidden in the efficiency of purification and decontamination at the right place during processing and to the necessary or desired extent.

Generally, the following applies: the sooner foreign substances are removed, in the process, and the more thoroughly this is done, the more efficient the process is.

The high plasticization temperature of PET in the range of 280°C is the reason why almost all common organic impurities such as PVC, PLA, polyolefin, chemical wood-pulp and paper fibers, polyvinyl acetate, melt adhesive, coloring agents, sugar and protein residues are transformed into colored degradation products which, in their turn, might release reactive degradation products additionally. Then, the number of defects in the polymer chain increases considerably. Naturally, the particle size distribution of impurities is very wide, the big particles of 60–1000 µm—which are visible by naked eye and easy to filter—representing the lesser evil since their total surface is relatively small and the degradation speed is therefore lower. The influence of the microscopic particles, which—because they are many—increase the frequency of defects in the polymer, is comparable bigger.

The motto "What the eye does not see the heart cannot grieve over" is considered to be very important in many recycling processes. Therefore besides efficient sorting the removal of visible impurity particles by melt filtration processes is playing a particular part in this case.

In general, one can say that the processes to make PET bottle flakes from collected bottles are as versatile as the different waste streams are different in their composition and quality. In view of technology there isn't just one way to do it. There are meanwhile many engineering companies which are offering flake production plants and components, and it is difficult to decide for one or other plant design. Nevertheless there are processes which are sharing most of these principles. Depending on composition and impurity level of input material, the general following process steps are applied.[16]
Bale opening, briquette opening
Sorting and selection for different colors, foreign polymers especially PVC, foreign matter, removal of film, paper, glass, sand, soil, stones and metals
Pre-washing without cutting
Coarse cutting dry or combined to pre-washing
Removal of stones, glass and metal
Air sifting to remove film, paper and labels
Grinding, dry and / or wet
Removal of low-density polymers (cups) by density differences
Hot wash
Caustic wash
Caustic surface etching, maintaining intrinsic viscosity and decontamination
Rinsing
Clean water rinsing
Drying
Air sifting of flakes
Automatic flake sorting
Water circuit and water treatment technology
Flake quality control

Impurities and material defects

The number of possible impurities and material defects which accumulate in the polymeric material is increasing permanently—when processing as well as when using polymers—taking into account a growing service life time, growing final applications and repeated recycling. As far as recycled PET bottles are concerned, the defects mentioned can be sorted in the following groups:

a) Reactive polyester OH- or COOH- end groups are transformed into dead or non-reactive end groups, e.g. formation of vinyl ester end groups through dehydration or decarboxylation of terephthalate acid, reaction of the OH- or COOH- end groups with mono-functional degradation products like mono-carbonic acids or alcohols. Results are decreased reactivity during re-polycondensation or re-SSP and broadening the molecular weight distribution.

b) The end group proportion shifts toward the direction of the COOH end groups built up through a thermal and oxidative degradation. The results are decrease in reactivity, and increase in the acid autocatalytic decomposition during thermal treatment in presence of humidity.

c) Number of poly-functional macromolecules increases. Accumulation of gels and long-chain branching defects.

d) Number, concentration and variety of non polymer-identical organic and inorganic foreign substances are increasing. With every new thermal stress, the organic foreign substances will react by decomposition. This is causing the liberation of further degradation-supporting substances and coloring substances.

e) Hydroxide and peroxide groups build up at the surface of the products made of polyester in presence of air (oxygen) and humidity. This process is accelerated by ultraviolet light. During an ulterior treatment process, hydro peroxides are a source of oxygen radicals which are source of oxidative degradation. Destruction of hydro peroxides is to happen before the first thermal treatment or during plasticization and can be supported by suitable additives like antioxidants.

Taking into consideration the above-mentioned chemical defects and impurities, there is an ongoing modification of the following polymer characteristics during each recycling cycle, which are detectable by chemical and physical laboratory analysis.

In particular:
Increase of COOH end groups
Increase of color number b
Increase of haze (transparent products)
Increase of oligomer content
Reduction in filterability
Increase of by-products content such as acetaldehyde, formaldehyde
Increase of extractable foreign contaminants
Decrease in color L
Decrease of intrinsic viscosity or dynamic viscosity
Decrease of crystallization temperature and increase of crystallization speed
Decrease of the mechanical properties like tensile strength, elongation at break or elastic modulus
Broadening of molecular weight distribution

The recycling of PET-bottles is meanwhile an industrial standard process which is offered by a wide variety of engineering companies.[17]

Processing examples for recycled polyester

Recycling processes with polyester are almost as varied as the manufacturing processes based on primary pellets or melt. Depending on purity of the recycled materials polyester can be used today in most of the polyester manufacturing processes as blend with virgin polymer or increasingly as 100% recycled polymer. Some exceptions like BOPET-film of low thickness, special applications like optical film or yarns through FDY-spinning at > 6000 m/min or microfilaments and micro-fibers are produced from virgin polyester only.

Simple re-pelletizing of bottle flakes

This process consists in transforming bottle waste into flakes, by drying and crystallizing the flakes, by plasticizing and filtering, as well as by pelletizing. Product is an amorphous re-granulate of an intrinsic viscosity in the range of 0.55–0.7 dℓ/g, depending on how complete pre-drying of PET flakes has been done.

Special feature are: acetaldehyde and oligomers are contained in the pellets at lower level; the viscosity is reduced somehow, the pellets are amorphous and have to be crystallized and dried before further processing.

Processing to:
A-PET film for thermoforming,
Addition to PET virgin production,
BoPET packaging film,
Bottle resin by SSP,
Carpet yarn,
Engineering plastics,
Filaments,
Non-woven,
Packaging stripes,
Staple fibre,

Choosing the re-pelletizing way means having an additional conversion process which is at the one side energy intensive, cost consuming and causes thermal destruction. At the other side the pelletizing step is providing the following advantages:
Intensive melt filtration
Intermediate quality control
Modification by additives.
Product selection and separation by quality
Processing flexibility increased
Quality uniformization
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Manufacture of PET-pellets for bottles (B-2-B) and A-PET

This process is, in principle, similar to the one described above; however, the pellets produced are directly (continuously or discontinuously) crystallized and then subjected to a solid-state polycondensation (SSP) in a tumbling drier or a vertical tube reactor. During this processing step, the corresponding intrinsic viscosity of 0.80 – 0.085 dℓ/g is rebuild again and, at the same time, the acetaldehyde content is reduced to < 1 ppm.

The fact that some machine manufacturers and line builders in Europe and USA make efforts to offer independent recycling processes, e.g. the so called bottle-to-bottle (B-2-B) process, such as URRC or BÜHLER, aims at generally furnishing proof of the "existence" of the required extraction residues and of the removal of model contaminants according to FDA applying the so called challenge test, which is necessary for the application of the treated polyester in the food sector. Besides this process approval it is nevertheless necessary that any user of such processes has to constantly check the FDA-limits for the raw materials manufactured by himself for his process.

Direct conversion of bottle flakes

In order to save costs, one is working on the direct use of the PET-flakes, from the treatment of used bottles, with a view to manufacturing an increasing number of polyester intermediates. For the adjustment of the necessary viscosity, besides an efficient drying of the flakes, it is possibly necessary to also reconstitute the viscosity through polycondensation in the melt phase or solid-state polycondensation of the flakes. The latest PET flake conversion processes are applying twin screw extruders, multi-screw extruders or multi-rotation systems and coincidental vacuum degassing to remove moisture and avoid flake pre-drying. These processes allow the conversion of undried PET flakes without substantial viscosity decrease caused by hydrolysis.

 Our USP :

• We make PET Jars and Bottles from Fully Automatic Stretch Blow Molding Machines
• Bottles and Jars from 10ml to 6 ltrs can been made
• Only food grade virgin materials are used
• Printing on jars is done by automatic machines
• We make both ROPP and CTC Neck Pet Preforms
• We also supply both Single-Piece and Double-Piece CTC Caps