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Thursday, October 12, 2023

Polyethylene terephthalate

From Wikipedia, the free encyclopedia

Polyethylene terephthalate
Strukturformel von Polyethylenterephthalat (PET)
PET polymer chain
A short section of a PET polymer chain
Names
IUPAC name
poly(ethylene terephthalate)
Systematic IUPAC name
poly(oxyethyleneoxyterephthaloyl)
Other names
Terylene (trademark); Dacron (trademark).
Identifiers
Abbreviations PET, PETE
ChEBI
ChemSpider
  • None
ECHA InfoCard 100.121.858 Edit this at Wikidata
UNII
Properties
(C10H8O4)n
Molar mass 10–50 kg/mol, varies
Density
Melting point > 250 °C (482 °F; 523 K) 260 °C
Boiling point > 350 °C (662 °F; 623 K) (decomposes)
Practically insoluble
log P 0.94540
Thermal conductivity 0.15 to 0.24 W/(m·K)
1.57–1.58, 1.5750
Thermochemistry
1.0 kJ/(kg·K)
Related compounds
Related Monomers
Terephthalic acid
Ethylene glycol

Polyethylene terephthalate (or poly(ethylene terephthalate), PET, PETE, or the obsolete PETP or PET-P), is the most common thermoplastic polymer resin of the polyester family and is used in fibres for clothing, containers for liquids and foods, and thermoforming for manufacturing, and in combination with glass fibre for engineering resins.

In 2016, annual production of PET was 56 million tons. The biggest application is in fibres (in excess of 60%), with bottle production accounting for about 30% of global demand. In the context of textile applications, PET is referred to by its common name, polyester, whereas the acronym PET is generally used in relation to packaging. Polyester makes up about 18% of world polymer production and is the fourth-most-produced polymer after polyethylene (PE), polypropylene (PP) and polyvinyl chloride (PVC).

PET consists of repeating (C10H8O4) units. PET is commonly recycled, and has the digit 1 (♳) as its resin identification code (RIC). The National Association for PET Container Resources (NAPCOR) defines PET as: "Polyethylene terephthalate items referenced are derived from terephthalic acid (or dimethyl terephthalate) and mono ethylene glycol, wherein the sum of terephthalic acid (or dimethyl terephthalate) and mono ethylene glycol reacted constitutes at least 90 percent of the mass of monomer reacted to form the polymer, and must exhibit a melting peak temperature between 225 °C and 255 °C, as identified during the second thermal scan in procedure 10.1 in ASTM D3418, when heating the sample at a rate of 10 °C/minute."

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 less than 500 nm) or opaque and white (particle size up to a few micrometers) depending on its crystal structure and particle size.

One process for making PET uses bis(2-hydroxyethyl) terephthalate, which can be synthesized by the esterification reaction between terephthalic acid and ethylene glycol with water as a byproduct (this is also known as a condensation reaction), or by transesterification reaction between ethylene glycol and dimethyl terephthalate (DMT) with methanol as a byproduct. Polymerization is through a polycondensation reaction of the monomers (done immediately after esterification/transesterification) with water as the byproduct.

Young's modulus, E 2800–3100 MPa
Tensile strength, σt 55–75 MPa
Elastic limit 50–150%
Notch test 3.6 kJ/m2
Glass transition temperature, Tg 67–81 °C
Vicat B 82 °C
Linear expansion coefficient, α 7×10−5 K−1
Water absorption (ASTM) 0.16

Uses

Textiles

Polyester fibres are widely used in the textile industry. The invention of the polyester fibre is attributed to J. R. Whinfield. It was first commercialized in the 1940s by ICI, under the brand 'Terylene'. Subsequently E. I. DuPont launched the brand 'Dacron'. As of 2022, there are many brands around the world, mostly Asian.

Polyester fibres are used in fashion apparel often blended with cotton, as heat insulation layers in thermal wear, sportswear and workwear and automotive upholstery.

Rigid packaging

Plastic bottles made from PET are widely used for soft drinks, both still and sparkling. For beverages that are degraded by oxygen, such as beer, a multilayer structure is used. PET sandwiches an additional polyvinyl alcohol (PVOH) or polyamide (PA) layer to further reduce its oxygen permeability.

Non-oriented PET sheet can be thermoformed to make packaging trays and blister packs. Crystallizable PET withstands freezing and oven baking temperatures. Both amorphous PET and BoPET are transparent to the naked eye. Color-conferring dyes can easily be formulated into PET sheet.

PET is permeable to oxygen and carbon dioxide and this imposes shelf life limitations of contents packaged in PET.

Flexible packaging

Biaxially oriented PET (BOPET) 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).

Photovoltaic modules

BOPET is used in the backsheet of photovoltaic modules. Most backsheets consist of a layer of BOPET laminated to a fluoropolymer or a layer of UV stabilized BOPET.

PET is also used as a substrate in thin film solar cells.

Thermoplastic resins

PET can be compounded with glass fibre and crystallization accelerators, to make thermoplastic resins. These can be injection moulded into parts such as housings, covers, electrical appliance components and elements of the ignition system.

Other applications

  • A waterproofing barrier in undersea cables.
  • As a film base.
  • As a fibre, spliced into bell rope tops to help prevent wear on the ropes as they pass through the ceiling.
  • Since late 2014 as liner material in type IV composite high pressure gas cylinders. PET works as a much better barrier to oxygen than earlier used (LD)PE.
  • As a 3D printing filament, as well as in the 3D printing plastic PETG (polyethylene terephthalate glycol). In 3D printing PETG has become a popular material - used for high-end applications like surgical fracture tables to automotive and aeronautical sectors, among other industrial applications. The surface properties can be modified to make PETG self-cleaning for applications like the fabrication of traffic signs for the manufacture of light-emitting diode LED spotlights.
  • As one of three layers for the creation of glitter; acting as a plastic core coated with aluminum and topped with plastic to create a light reflecting surface, although as of 2021 many glitter manufacturing companies have begun to phase out the use of PET after calls from organizers of festivals to create bio-friendly glitter alternatives.
  • Film for tape applications, such as the carrier for magnetic tape or backing for pressure-sensitive adhesive tapes. Digitalization has caused the virtual disappeance of the magnetic audio and videotape application.
  • Water-resistant paper.

History

PET was patented in 1941 by John Rex Whinfield, James Tennant Dickson and their employer the Calico Printers' Association of Manchester, England. E. I. DuPont de Nemours in Delaware, United States, first used the trademark Mylar in June 1951 and received registration of it in 1952. It is still the best-known name used for polyester film. The current owner of the trademark is DuPont Teijin Films.

In the Soviet Union, PET was first manufactured in the laboratories of the Institute of High-Molecular Compounds of the USSR Academy of Sciences in 1949, and its name "Lavsan" is an acronym thereof (лаборатории Института высокомолекулярных соединений Академии наук СССР).

The PET bottle was invented in 1973 by Nathaniel Wyeth and patented by DuPont.

Physical properties

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 in its most stable state is a colorless, semi-crystalline resin. However it is intrinsically slow to crystallize compared to other semicrystalline polymers. Depending on processing conditions it can be formed into either amorphous or crystalline articles. Its amenability to drawing makes PET useful in fibre and film applications. Like most aromatic polymers, it has better barrier properties than aliphatic polymers. It is strong and impact-resistant. PET is hygroscopic.

About 60% crystallization is the upper limit for commercial products, with the exception of polyester fibers. Transparent products can be produced by rapidly cooling molten polymer below Tg glass transition temperature to form an amorphous solid. Like glass, amorphous PET forms when its molecules are not given enough time to arrange themselves in an orderly, crystalline 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 by heating above Tg, they begin to move again, allowing crystals to nucleate and grow. This procedure is known as solid-state crystallization.

When allowed to cool slowly, the molten polymer forms a more crystalline material. This material has spherulites containing 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, causing the resulting solid to be translucent.

Orientation also renders polymers more transparent. This is why BOPET film and bottles are both crystalline to a degree and transparent.

Amorphous PET crystallizes and becomes opaque when exposed to solvents such as chloroform or toluene.

PET is stoichiometrically a mixture of carbon and H2O, and therefore has been used in an experiment involving laser-driven shock compression which created nanodiamonds and superionic water. This could be a possible way of producing nanodiamonds commercially.

Absorption/scalping

PET has an affinity for hydrophobic flavors, and drinks sometimes need to be formulated with a higher flavor dosage, compared to those going into glass, to offset the flavor taken up by the container. Heavy gauge PET bottles are sometimes returnable for re-use as is practiced in some EU countries, however the propensity of PET to absorb flavors makes it necessary to conduct a "sniffer" test on returned bottles to avoid cross-contamination of flavors.

Intrinsic viscosity

Different applications of PET require different degrees of polymerization, which can be obtained by modifying the process conditions. The molecular weight of PET is measured by solution viscosity. The preferred method is intrinsic viscosity (IV).

IV is a dimensionless measurement. It is found by extrapolating the relative viscosity (measured in (dℓ/g)) to zero concentration.

Shown below are the IV ranges for the main applications:

Fibers
  • 0.40–0.70: textile
  • 0.72–0.98: technical eg tire cord
Films
Bottles
  • 0.70–0.78: general purpose bottles
  • 0.78–0.85: bottles for carbonated drinks
Monofilaments, engineering plastics
  • 1.00–2.00

Copolymers

PET is copolymerized with other diols or diacids to optimize the properties for particular applications.

For example, cyclohexanedimethanol (CHDM) can be added to the polymer backbone in place of ethylene glycol. Since this building block is much larger (six 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. In general, such PET is known as PETG or PET-G (polyethylene terephthalate glycol-modified). It is a clear amorphous thermoplastic that can be injection-molded, sheet-extruded or extruded as filament for 3D printing. PETG 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 co-PET film, or amorphous PET sheet (A-PET/PETA) 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 isophthalic acid, CHDM, diethylene glycol (DEG) 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.

Production

Polyethylene terephthalate is produced from ethylene glycol (usually referred to in the trade as "MEG", for monoethylene glycol) and dimethyl terephthalate (DMT) (C6H4(CO2CH3)2) but mostly terephthalic acid (known in the trade as "PTA", for purified terephthalic acid). As of 2022, ethylene glycol is made from ethene found in natural gas, while terephthalic acid comes from p-xylene made from crude oil. Typically an antimony or titanium compound is used as a catalyst, a phosphite is added as a stabilizer and a bluing agent such as cobalt salt is added to mask any yellowing.

Dimethyl terephthalate (DMT) process

Polyesterification reaction in the production of PET

In the dimethyl terephthalate (DMT) process, DMT and excess MEG are transesterified in the melt at 150–200 °C with a basic catalyst. Methanol (CH3OH) is removed by distillation to drive the reaction forward. Excess MEG is distilled off at higher temperature with the aid of vacuum. The second transesterification step proceeds at 270–280 °C, with continuous distillation of MEG as well.

The reactions can be summarized as follows:

First step
C6H4(CO2CH3)2 + 2 HOCH2CH2OH → C6H4(CO2CH2CH2OH)2 + 2 CH3OH
Second step
n C6H4(CO2CH2CH2OH)2 → [(CO)C6H4(CO2CH2CH2O)]n + n HOCH2CH2OH

Terephthalic acid (PTA) process

Polycondensation reaction in the production of PET

In the terephthalic acid process, MEG and PTA are esterified directly at moderate pressure (2.7–5.5 bar) and high temperature (220–260 °C). Water is eliminated in the reaction, and it is also continuously removed by distillation:

n C6H4(CO2H)2 + n HOCH2CH2OH → [(CO)C6H4(CO2CH2CH2O)]n + 2n H2O

Bio-PET

Bio-PET is the bio-based counterpart of PET. Essentially in Bio-PET, the MEG is manufactured from ethylene derived from sugar cane ethanol. A better process based on oxidation of ethanol has been proposed, and it is also technically possible to make PTA from readily available biobased furfural.

Degradation

PET is subject to degradation during processing. If the moisture level is too high, hydrolysis will reduce the molecular weight by chain scission, resulting in brittleness.

If the residence time and/or melt temperature are too high, then thermal degradation or thermooxidative degradation will occur resulting in:

Mitigation measures include

Acetaldehyde

Acetaldehyde is a colorless, volatile substance with a fruity smell. Although it forms naturally in some fruit, it can cause an off-taste in bottled water. Acetaldehyde forms by degradation of PET through the mishandling 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. Photo-oxidation can also cause the gradual formation acetaldehyde over the object's lifespan. This proceeds via a Type II Norrish reaction.

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.

Biodegradation

At least one species of bacterium in the genus Nocardia can degrade PET with an esterase enzyme. Esterases are enzymes able to cleave the ester bond. Also, the initial degradation of PET can be esterases expressed by Bacillus and Nocardia.

Japanese scientists have isolated a bacterium Ideonella sakaiensis that possesses two enzymes which can break down the PET into smaller pieces that the bacterium can digest. A colony of I. sakaiensis can disintegrate a plastic film in about six weeks.

French researchers report developing an improved PET hydrolase that can depolymerize at least 90 percent of PET in 10 hours, breaking it down into monomers.

An enzyme based on a natural PET-ase was designed with the help of a machine learning algorithm to be able to tolerate pH and temperature changes by the University of Texas at Austin. The PET-ase was found to able to degrade various products and could break them down as fast as 24 hours.

Environmental concerns

Resource depletion

Compared to the use of petroleum as fuel, however, the amount of crude oil processed into PET is very small. The total production capacity of PET is around 30 million tons, compared to 4.2 billion tons of crude oil production, thus around 0.7% of crude oil is processed into PET.

End of life

Recycle

PET bottles lend themselves well to recycling (see below). In many countries PET bottles are recycled to a substantial degree, for example about 75% in Switzerland. The term rPET is commonly used to describe the recycled material, though it is also referred to as R-PET or post-consumer PET (POSTC-PET).

Energy recovery

PET is a desirable fuel for waste-to-energy plants, as it has a high calorific value which helps to reduce the use of primary resources for energy generation.

Littering

Nevertheless, littering has become a prominent issue in public opinion, and PET bottles are a visible part of that.

Dumping of apparel

A substantial amount of post consumer waste from the textile industry ends up in landfills in developing countries such as Chile and in countries in West Africa such as Ghana. PET being a substantial component of apparel, this waste in landfills contains much PET.

Microfibres from apparel and microplastics

Clothing sheds microfibres in use, during washing and machine drying. Plastic litter slowly forms small particles. Microplastics which are present on the bottom of the river or seabed can be ingested by small marine life, thus entering the food chain. As PET has a higher density than water, a significant amount of PET microparticles may be precipitated in sewage treatment plants. PET microfibers generated by apparel wear, washing or machine drying can become airborne, and be dispersed into fields, where they are ingested by livestock or plants and end up in the human food supply. SAPEA have declared that such particles 'do not pose a widespread risk'. PET is known to degrade when exposed to sunlight and oxygen. As of 2016, scarce information exists regarding the life-time of the synthetic polymers in the environment.

Safety

Commentary published in Environmental Health Perspectives in April 2010 suggested that PET might yield endocrine disruptors under conditions of common use and recommended research on this topic. Proposed mechanisms include leaching of phthalates as well as leaching of antimony. An article published in Journal of Environmental Monitoring in April 2012 concludes that antimony concentration in deionized water stored in PET bottles stays within EU's acceptable limit even if stored briefly at temperatures up to 60 °C (140 °F), while bottled contents (water or soft drinks) may occasionally exceed the EU limit after less than a year of storage at room temperature.

Antimony

Antimony (Sb) is a metalloid element that is used as a catalyst in the form of compounds such 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 US EPA maximum contamination levels. The drinking water limit assessed by WHO is 20 parts per billion (WHO, 2003), and the drinking water limit in the United States is 6 parts per billion. Although antimony trioxide is of low toxicity when taken orally, 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. The WHO has published a risk assessment for antimony in drinking water.

Fruit juice concentrates (for which no guidelines are established), however, that were produced and bottled in PET in the UK were found to contain up to 44.7 μg/L of antimony, well above the EU limits for tap water of 5 μg/L.

Bottle processing equipment

A finished PET drink bottle compared to the preform from which it is made

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 step, 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 robust and unique containers themselves; besides novelty candy, some Red Cross chapters distribute them as part of the Vial of Life program to homeowners to store medical history for emergency responders.

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

Resin identification code 1
Alternate 1
Alternate 2

Worldwide, 480 billion plastic drinking bottles were made in 2016 (and less than half were recycled).

While most thermoplastics can, in principle, be recycled, PET bottle recycling is more practical than many other plastic applications because of the high value of the resin and the almost exclusive use of PET for widely used water and carbonated soft drink bottling. The prime uses for recycled PET are polyester fiber, strapping, and non-food containers.

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. 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, like 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).

When recycling polyethylene terephthalate or PET or polyester, in general three ways have to be differentiated:

  1. 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(2-hydroxyethyl) terephthalate
  2. The mechanical recycling where the original polymer properties are being maintained or reconstituted.
  3. The chemical recycling where transesterification takes place and other glycols/polyols or glycerol are added to make a polyol which may be used in other ways such as polyurethane production or PU foam production In addition, PET can even be recycled chemically into epoxy based products including paints.

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 breakthrough 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-size industry. Cost-efficiency can already be achieved with plant capacities within a range of 5000–20,000 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 by 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 the 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.

PET bottle recycling

The only form of PET that is widely recycled in 2022 is the bottle. These are recycled by 'mechanical recycling' increasingly to bottles but still to other forms such as film or fibre. Other forms of polyester are not (as of 2022) collected in significant quantities.

Significant investments were announced in 2021 and 2022 for chemical recycling of PET by glycolysis, methanolysis and enzymatic recycling to recover monomers. Initially these will also use bottles as feedstock but it is expected that fibres will also be recycled this way in future.

 

Chain mail

From Wikipedia, the free encyclopedia
A European mail shirt.

Chain mail is the name (also known as mail or maille, but also called chain mail or chainmail) of a type of armour consisting of small metal rings linked together in a pattern to form a mesh. It was in common military use between the 3rd century BC and the 16th century AD in Europe, while still being used in Asia, Africa, and the Middle East. A coat of this armour is often called a hauberk or sometimes a byrnie.

History

The Vachères warrior, 1st century BC, a statue depicting a Romanized Gaulish warrior wearing mail and a Celtic torc around his neck, bearing a Celtic-style shield.
Fresco of an ancient Macedonian soldier (thorakites) wearing mail armour and bearing a thureos shield

The earliest examples of surviving mail were found in the Carpathian Basin at a burial in Horný Jatov, Slovakia dated in the 3rd century BC, and in a chieftain's burial located in Ciumești, Romania. Its invention is commonly credited to the Celts, but there are examples of Etruscan pattern mail dating from at least the 4th century BC. Mail may have been inspired by the much earlier scale armour. Mail spread to North Africa, West Africa, the Middle East, Central Asia, India, Tibet, South East Asia, and Japan.

Herodotus wrote that the ancient Persians wore scale armour, but mail is also distinctly mentioned in the Avesta, the ancient holy scripture of the Persian religion of Zoroastrianism that was founded by the prophet Zoroaster in the 5th century BC.

Mail continues to be used in the 21st century as a component of stab-resistant body armour, cut-resistant gloves for butchers and woodworkers, shark-resistant wetsuits for defense against shark bites, and a number of other applications.

Etymology

The origins of the word mail are not fully known. One theory is that it originally derives from the Latin word macula, meaning spot or opacity (as in macula of retina). Another theory relates the word to the old French maillier, meaning to hammer (related to the modern English word malleable). In modern French, maille refers to a loop or stitch. The Arabic words "burnus", برنوس, a burnoose; a hooded cloak, also a chasuble (worn by Coptic priests) and "barnaza", برنز, to bronze, suggest an Arabic influence for the Carolingian armour known as "byrnie" (see below).

The first attestations of the word mail are in Old French and Anglo-Norman: maille, maile, or male or other variants, which became mailye, maille, maile, male, or meile in Middle English.

In early medieval Europe "byrn(ie)" was the equivalent of a "coat of mail"

Civilizations that used mail invented specific terms for each garment made from it. The standard terms for European mail armour derive from French: leggings are called chausses, a hood is a mail coif, and mittens, mitons. A mail collar hanging from a helmet is a camail or aventail. A shirt made from mail is a hauberk if knee-length and a haubergeon if mid-thigh length. A layer (or layers) of mail sandwiched between layers of fabric is called a jazerant.

A waist-length coat in medieval Europe was called a byrnie, although the exact construction of a byrnie is unclear, including whether it was constructed of mail or other armour types. Noting that the byrnie was the "most highly valued piece of armour" to the Carolingian soldier, Bennet, Bradbury, DeVries, Dickie, and Jestice indicate that:

There is some dispute among historians as to what exactly constituted the Carolingian byrnie. Relying... only on artistic and some literary sources because of the lack of archaeological examples, some believe that it was a heavy leather jacket with metal scales sewn onto it. It was also quite long, reaching below the hips and covering most of the arms. Other historians claim instead that the Carolingian byrnie was nothing more than a coat of mail, but longer and perhaps heavier than traditional early medieval mail. Without more certain evidence, this dispute will continue.

In Europe

Mail armour and equipment of Polish medium cavalryman, from the second half of the 17th century

The use of mail as battlefield armour was common during the Iron Age and the Middle Ages, becoming less common over the course of the 16th and 17th centuries when plate armour and more advanced firearms were developed. It is believed that the Roman Republic first came into contact with mail fighting the Gauls in Cisalpine Gaul, now Northern Italy. The Roman army adopted the technology for their troops in the form of the lorica hamata which was used as a primary form of armour through the Imperial period.

Panel from the Bayeux Tapestry showing Norman and Anglo-Saxon soldiers in mail armour. Note the scene of stripping a mail hauberk from the dead at the bottom.

After the fall of the Western Empire, much of the infrastructure needed to create plate armour diminished. Eventually the word "mail" came to be synonymous with armour. It was typically an extremely prized commodity, as it was expensive and time-consuming to produce and could mean the difference between life and death in a battle. Mail from dead combatants was frequently looted and was used by the new owner or sold for a lucrative price. As time went on and infrastructure improved, it came to be used by more soldiers. The oldest intact mail hauberk still in existence is thought to have been worn by Leopold III, Duke of Austria, who died in 1386 during the Battle of Sempach. Eventually with the rise of the lanced cavalry charge, impact warfare, and high-powered crossbows, mail came to be used as a secondary armour to plate for the mounted nobility.

By the 14th century, articulated plate armour was commonly used to supplement mail. Eventually mail was supplanted by plate for the most part, as it provided greater protection against windlass crossbows, bludgeoning weapons, and lance charges while maintaining most of the mobility of mail. However, it was still widely used by many soldiers, along with brigandines and padded jacks. These three types of armour made up the bulk of the equipment used by soldiers, with mail being the most expensive. It was sometimes more expensive than plate armour. Mail typically persisted longer in less technologically advanced areas such as Eastern Europe but was in use throughout Europe into the 16th century.

During the late 19th and early 20th century, mail was used as a material for bulletproof vests, most notably by the Wilkinson Sword Company. Results were unsatisfactory; Wilkinson mail worn by the Khedive of Egypt's regiment of "Iron Men" was manufactured from split rings which proved to be too brittle, and the rings would fragment when struck by bullets and aggravate the injury. The riveted mail armour worn by the opposing Sudanese Madhists did not have the same problem but also proved to be relatively useless against the firearms of British forces at the battle of Omdurman. During World War I, Wilkinson Sword transitioned from mail to a lamellar design which was the precursor to the flak jacket.

a mask with a leather upper with slits on the metal eyepieces, and a chain mail lower, modelled on a dummy head with a metal war helmet
WWI Splatter Mask on display at the Army Medical Services Museum

Chain mail was also used for face protection in World War I. Oculist Captain Cruise of the British Infantry designed a mail fringe to be attached to helmets to protect the upper face. This proved unpopular with soldiers, in spite of being proven to defend against a three-ounce (100 g) shrapnel round fired at a distance of one hundred yards (91 m). Another invention, a "splatter mask" or "splinter mask", consisted of rigid upper face protection and a mail veil to protect the lower face, and was used by early tank crews as a measure against flying steel fragments (spalling) inside the vehicle.

In Asia

Tibetan warrior in mail reinforced by additional mirror plate

Mail armour was introduced to the Middle East and Asia through the Romans and was adopted by the Sassanid Persians starting in the 3rd century AD, where it was supplemental to the scale and lamellar armour already used. Mail was commonly also used as horse armour for cataphracts and heavy cavalry as well as armour for the soldiers themselves. Asian mail could be just as heavy as the European variety and sometimes had prayer symbols stamped on the rings as a sign of their craftsmanship as well as for divine protection.

Mail armour is mentioned in the Quran as being a gift revealed by Allah to David:

21:80 It was We Who taught him the making of coats of mail for your benefit, to guard you from each other's violence: will ye then be grateful? (Yusuf Ali's translation)

Mughal Army

From the Abbasid Caliphate, mail was quickly adopted in Central Asia by Timur (Tamerlane) and the Sogdians and by India's Delhi Sultanate. Mail armour was introduced by the Turks in late 12th century and commonly used by Turk and the Mughal and Suri armies where it eventually became the armour of choice in India. Indian mail was constructed with alternating rows of solid links and round riveted links and it was often integrated with plate protection (mail and plate armour).

China

Mail was introduced to China when its allies in Central Asia paid tribute to the Tang Emperor in 718 by giving him a coat of "link armour" assumed to be mail. China first encountered the armour in 384 when its allies in the nation of Kuchi arrived wearing "armour similar to chains". Once in China, mail was imported but was not produced widely. Due to its flexibility, comfort, and rarity, it was typically the armour of high-ranking guards and those who could afford the exotic import (to show off their social status) rather than the armour of the rank and file, who used more common brigandine, scale, and lamellar types. However, it was one of the few military products that China imported from foreigners. Mail spread to Korea slightly later where it was imported as the armour of imperial guards and generals.

Japan

Edo period Japanese (samurai) chain armour or kusari gusoku

In Japan, mail is called kusari which means chain. When the word kusari is used in conjunction with an armoured item it usually means that mail makes up the majority of the armour composition. An example of this would be kusari gusoku which means chain armour. Kusari jackets, hoods, gloves, vests, shin guards, shoulder guards, thigh guards, and other armoured clothing were produced, even kusari tabi socks.

Kusari was used in samurai armour at least from the time of the Mongol invasion (1270s) but particularly from the Nambokucho Period (1336–1392). The Japanese used many different weave methods including a square 4-in-1 pattern (so gusari), a hexagonal 6-in-1 pattern (hana gusari) and a European 4-in-1 (nanban gusari). The rings of Japanese mail were much smaller than their European counterparts; they would be used in patches to link together plates and to drape over vulnerable areas such as the armpits.

Riveted kusari was known and used in Japan. On page 58 of the book Japanese Arms & Armor: Introduction by H. Russell Robinson, there is a picture of Japanese riveted kusari, and this quote from the translated reference of Sakakibara Kozan's 1800 book, The Manufacture of Armour and Helmets in Sixteenth-Century Japan, shows that the Japanese not only knew of and used riveted kusari but that they manufactured it as well.

... karakuri-namban (riveted namban), with stout links each closed by a rivet. Its invention is credited to Fukushima Dembei Kunitaka, pupil, of Hojo Awa no Kami Ujifusa, but it is also said to be derived directly from foreign models. It is heavy because the links are tinned (biakuro-nagashi) and these are also sharp-edged because they are punched out of iron plate

Butted or split (twisted) links made up the majority of kusari links used by the Japanese. Links were either butted together meaning that the ends touched each other and were not riveted, or the kusari was constructed with links where the wire was turned or twisted two or more times; these split links are similar to the modern split ring commonly used on keychains. The rings were lacquered black to prevent rusting, and were always stitched onto a backing of cloth or leather. The kusari was sometimes concealed entirely between layers of cloth.

Kusari gusoku or chain armour was commonly used during the Edo period 1603 to 1868 as a stand-alone defense. According to George Cameron Stone

Entire suits of mail kusari gusoku were worn on occasions, sometimes under the ordinary clothing

In his book Arms and Armor of the Samurai: The History of Weaponry in Ancient Japan, Ian Bottomley shows a picture of a kusari armour and mentions kusari katabira (chain jackets) with detachable arms being worn by samurai police officials during the Edo period. The end of the samurai era in the 1860s, along with the 1876 ban on wearing swords in public, marked the end of any practical use for mail and other armour in Japan. Japan turned to a conscription army and uniforms replaced armour.

Effectiveness

Mail hauberk from the Museum of Bayeux

Mail's resistance to weapons is determined by four factors: linkage type (riveted, butted, or welded), material used (iron versus bronze or steel), weave density (a tighter weave needs a thinner weapon to surpass), and ring thickness (generally ranging from 1.0–1.6 mm diameter (18 to 14 gauge) wire in most examples). Mail, if a warrior could afford it, provided a significant advantage when combined with competent fighting techniques.

When the mail was not riveted, a thrust from most sharp weapons could penetrate it. However, when mail was riveted, only a strong well-placed thrust from certain spears, or thin or dedicated mail-piercing swords like the estoc, could penetrate, and a pollaxe or halberd blow could break through the armour. Strong projectile weapons such as stronger self bows, recurve bows, and crossbows could also penetrate riveted mail. Some evidence indicates that during armoured combat, the intention was to actually get around the armour rather than through it—according to a study of skeletons found in Visby, Sweden, a majority of the skeletons showed wounds on less well protected legs. Although mail was a formidable protection, due to technological advances as time progressed, mail worn under plate armour (and stand-alone mail as well) could be penetrated by the conventional weaponry of another knight.

The flexibility of mail meant that a blow would often injure the wearer, potentially causing serious bruising or fractures, and it was a poor defence against head trauma. Mail-clad warriors typically wore separate rigid helms over their mail coifs for head protection. Likewise, blunt weapons such as maces and warhammers could harm the wearer by their impact without penetrating the armour; usually a soft armour, such as gambeson, was worn under the hauberk. Medieval surgeons were very well capable of setting and caring for bone fractures resulting from blunt weapons. With the poor understanding of hygiene, however, cuts that could get infected were much more of a problem. Thus mail armour proved to be sufficient protection in most situations.

Manufacture

A manuscript from 1698 showing the manufacture of mail

Several patterns of linking the rings together have been known since ancient times, with the most common being the 4-to-1 pattern (where each ring is linked with four others). In Europe, the 4-to-1 pattern was completely dominant. Mail was also common in East Asia, primarily Japan, with several more patterns being utilised and an entire nomenclature developing around them.

Historically, in Europe, from the pre-Roman period on, the rings composing a piece of mail would be riveted closed to reduce the chance of the rings splitting open when subjected to a thrusting attack or a hit by an arrow.

Up until the 14th century European mail was made of alternating rows of round riveted rings and solid rings. Sometime during the 14th century European mail makers started to transition from round rivets to wedge shaped rivets but continued using alternating rows of solid rings. Eventually European mail makers stopped using solid rings and almost all European mail was made from wedge riveted rings only with no solid rings. Both were commonly made of wrought iron, but some later pieces were made of heat-treated steel. Wire for the riveted rings was formed by either of two methods. One was to hammer out wrought iron into plates and cut or slit the plates. These thin pieces were then pulled through a draw plate repeatedly until the desired diameter was achieved. Waterwheel powered drawing mills are pictured in several period manuscripts. Another method was to simply forge down an iron billet into a rod and then proceed to draw it out into wire. The solid links would have been made by punching from a sheet. Guild marks were often stamped on the rings to show their origin and craftsmanship. Forge welding was also used to create solid links, but there are few possible examples known; the only well documented example from Europe is that of the camail (mail neck-defence) of the 7th century Coppergate helmet. Outside of Europe this practice was more common such as "theta" links from India. Very few examples of historic butted mail have been found and it is generally accepted that butted mail was never in wide use historically except in Japan where mail (kusari) was commonly made from butted links. Butted link mail was also used by the Moros of the Philippines in their mail and plate armours.

Modern uses

Practical uses

Neptunic shark suit

Mail is used as protective clothing for butchers against meat-packing equipment. Workers may wear up to 4 kg (8 lb) of mail under their white coats. Butchers also commonly wear a single mail glove to protect themselves from self-inflicted injury while cutting meat, as do many oyster shuckers.

Scuba divers sometimes use mail to protect them from sharkbite, as do animal control officers for protection against the animals they handle. In 1980, marine biologist Jeremiah Sullivan patented his design for Neptunic full coverage chain mail shark resistant suits which he had developed for close encounters with sharks. Shark expert and underwater filmmaker Valerie Taylor was among the first to develop and test shark suits in 1979 while diving with sharks.

Mail is widely used in industrial settings as shrapnel guards and splash guards in metal working operations.

Electrical applications for mail include RF leakage testing and being worn as a Faraday cage suit by tesla coil enthusiasts and high voltage electrical workers.

Stab-proof vests

Conventional textile-based ballistic vests are designed to stop soft-nosed bullets but offer little defense from knife attacks. Knife-resistant armour is designed to defend against knife attacks; some of these use layers of metal plates, mail and metallic wires.

Historical re-enactment

Roman soldier 175 A.D. from a northern province (re-enactment).

Many historical reenactment groups, especially those whose focus is Antiquity or the Middle Ages, commonly use mail both as practical armour and for costuming. Mail is especially popular amongst those groups which use steel weapons. A modern hauberk made from 1.5 mm diameter wire with 10 mm inner diameter rings weighs roughly 10 kg (22 lb) and contains 15,000–45,000 rings.

One of the drawbacks of mail is the uneven weight distribution; the stress falls mainly on shoulders. Weight can be better distributed by wearing a belt over the mail, which provides another point of support.

Mail worn today for re-enactment and recreational use can be made in a variety of styles and materials. Most recreational mail today is made of butted links which are galvanised or stainless steel. This is historically inaccurate but is much less expensive to procure and especially to maintain than historically accurate reproductions. Mail can also be made of titanium, aluminium, bronze, or copper. Riveted mail offers significantly better protection ability as well as historical accuracy than mail constructed with butted links. Japanese mail (kusari) is one of the few historically correct examples of mail being constructed with such butted links.

Decorative uses

Major's shoulder chains
A modern example of the use of mail, a bracelet using the roundmaille weave

Mail remained in use as a decorative and possibly high-status symbol with military overtones long after its practical usefulness had passed. It was frequently used for the epaulettes of military uniforms. It is still used in this form by some regiments of the British Army.

Mail has applications in sculpture and jewellery, especially when made out of precious metals or colourful anodized metals. Mail artwork includes headdresses, decorative wall hangings, ornaments, chess sets, macramé, and jewelry. For these non-traditional applications, hundreds of patterns (commonly referred to as "weaves") have been invented.

Large-linked mail is occasionally used as a fetish clothing material, with the large links intended to reveal – in part – the body beneath them.

In film

In some films, knitted string spray-painted with a metallic paint is used instead of actual mail in order to cut down on cost (an example being Monty Python and the Holy Grail, which was filmed on a very small budget). Films more dedicated to costume accuracy often use ABS plastic rings, for the lower cost and weight. Such ABS mail coats were made for The Lord of the Rings film trilogy, in addition to many metal coats. The metal coats are used rarely because of their weight, except in close-up filming where the appearance of ABS rings is distinguishable. A large scale example of the ABS mail used in the Lord of the Rings can be seen in the entrance to the Royal Armouries museum in Leeds in the form of a large curtain bearing the logo of the museum. It was acquired from the makers of the film's armour, Weta Workshop, when the museum hosted an exhibition of WETA armour from their films. For the film Mad Max Beyond Thunderdome, Tina Turner is said to have worn actual mail and she complained how heavy this was. Game of Thrones makes use of mail, notably during the "Red Wedding" scene.

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