Thermoplastic
Thermoplastic, also known as a thermosoftening plastic, is a polymer that turns to a liquid when heated and freezes to a rigid state when cooled sufficiently. Most thermoplastics are high-molecular-weight polymers whose chains associate through weak van der waals forces (polyethylene); stronger dipole-dipole interactions and hydrogen bonding(nylon); or even stacking of aromatic rings (polystyrene). Thermoplastic polymers differ from thermosetting polymers(e.g phenolics, epoxies) in that they can be remelted and remoulded. Many thermoplastic materials are additionpolymers; e.g., vinyl chain-growth polymers such as polyethylene and polypropylene; others are productions of condensation or other forms of polyaddition polymerisation, such as the polyamides or polyesters
Theory
Thermoplastics are elastic and flexible above a glass transition temperature Tg, specific for each one — the midpoint of a temperature range in contrast to the sharp melting point of a pure crystalline substance like water. Below a second, higher melting temperature, Tm, also the midpoint of a range, some thermoplastics have crystalline regions alternating with amorphous regions in which the chains approximate random coils. The amorphous regions contribute elasticity and the crystalline regions contribute strength and rigidity, as is also the case for non-thermoplastic fibrous protenis such as silk. (Elasticity does not mean they are particularly stretchy; e.g., polyamides/Nylons rope and fishing line.) Above Tm all crystalline structure disappears and the chains become randomly inter dispersed. As the temperature increases above Tm, viscosity gradually decreases without any distinct phasechange.
Some thermoplastics normally do not
crystallize: they are termed "amorphous" plastics and are useful at
temperatures below the Tg.
They are frequently used in applications where clarity is important. Some
typical examples of amorphous thermoplastics are PMMA, PS, and PC.
Generally, amorphous thermoplastics are less chemically resistant and can be
subject to environmental stress cracking.
Thermoplastics will crystallize to a certain extent and are called
"semi-crystalline" for this reason. Typical semi-crystalline
thermoplastics are PE,PP,PBT andPET. The speed and extent to which
crystallization can occur depends in part on the flexibility of the polymer
chain. Semi-crystalline thermoplastics are more resistant to solvents and other
chemicals. If the crystallites are larger than the wavelength of light, the
thermoplastic is hazy or opaque.
Semi-crystalline thermoplastics become less
brittle above 'T'g. If a plastic with otherwise desirable properties
has too high a Tg,
it can often be lowered by adding a relatively low molecular weight plasticizer to the melt before forming (plastics extrusion; moulding) and cooling. A similar result can sometimes be achieved by adding non-reactive side chains to the monomers before polymeriztion.
Both methods make the polymer chains stand off a bit from one another. Before
the introduction of plasticizers, plastic automobile parts often cracked in cold winter weather.
Another method of lowering Tg (or raising Tm) is to
incorporate the original plastic into a copolymer,
as with graft copolymer of
polystyrene, or into a composite material. Lowering Tg is not the only way to reduce
brittleness. Drawing (and
similar processes that stretch or orient the molecules) or increasing the
length of the polymer chains also decrease brittleness.
Thermoplastics can go through
melting/freezing cycles repeatedly and the fact that they can be reshaped upon
reheating gives them their name. This quality makes thermoplastics recyclable.
The processes required for recycling vary with the thermoplastic. The plastics
used for soda bottles are a common example of thermoplastics that can be and
are widely recycled. Animal horn,
made of the protein keratene,
softens on heating, is somewhat reshapable, and may be regarded as a natural,
quasi-thermoplastic material.
Although modestly vulcanized natural and
synthetic rubbers are stretchy, they are elastomeric thermosets, not thermoplastics. Each
has its own Tg,
and will crack and shatter when cold enough so that the crosslinked polymer chains can no longer move
relative to one another. But they have no Tm and will decompose at high
temperatures rather than melt. Recently, thermoplastic elastomers have become available.
Melting point and glass transition
temperature of various thermoplastics
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Polymer
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Tm
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Tg
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Acrylic (PMMA)
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130–140 °C
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Cyclic Olefin Copolymer (COC)
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Ethylene-Vinyl Acetate (EVA)
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Ethylene vinyl alcohol (EVOH)
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Fluoroplastics (PTFE, alongside with
FEP, PFA,CTFE, ECTFE, ETFE)
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Liquid Crystal Polymer (LCP)
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Polyoxymethylene (POM or Acetal)
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175°C
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Polyacrylates (Acrylic)
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Polyacrylonitrile (PAN or Acrylonitrile)
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Polyamide (PA or Nylon)
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Polyamide-imide (PAI)
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Polyaryletherketone (PAEK or Ketone)
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Polybutadiene (PBD)
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Polybutylene (PB)
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225°C
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40°C
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Polycaprolactone (PCL)
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62 °C
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Polychlorotrifluoroethylene (PCTFE)
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255 °C
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75 °C
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Polycyclohexylene
dimethylene terephthalate (PCT)
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Polycarbonate (PC)
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267 °C
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Polyhydroxyalkanoates (PHAs)
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145|
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Polyketone (PK)
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260 C
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75 C
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Polyethylene (PE)
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105–130 °C
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-127 °C
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Polyetheretherketone (PEEK)
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343 °C
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143 °C
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Polyetherketoneketone (PEKK)
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Polyetherimide (PEI)
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Polyethersulfone (PES)- see Polysulfone
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Chlorinated
Polyethylene (CPE)
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Polyimide (PI)
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Polylactic
acid (PLA)
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50–80 °C
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Polymethylpentene (PMP)
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Polyphenylene oxide (PPO)
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Polyphenylene sulfide (PPS)
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Polyphthalamide (PPA)
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Polypropylene (PP)
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160 °C
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Polystyrene (PS)
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240 °C
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Polysulfone (PSU)
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Polyurethane (PU)
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Polyvinyl acetate (PVA)
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32 °C
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Polyvinyl chloride (PVC)
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80 °C
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Polyvinylidene chloride (PVDC)
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185 °C
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40 °C
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Styrene-acrylonitrile (SAN)
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115|
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Terminology
The literature on thermoplastics is huge, and
can be quite confusing, as the same chemical can be available in many different
forms (for example, at different molecular weight), which might have quite different physical properties. The
same chemical can be referred to by many different tradenames, by different
abbreviations; two chemical compounds can share the same name; a good example
of the latter is the word "Teflon" which is used to refer to a
specific polymer (PTFE); to related polymers such as PFA, and generically to fluoropolymer
Testing
Testing of thermoplastics can take various
forms.
Tensile tests—ISO
527 -1/-2 and ASTM D 638 set out the standardized test methods. These standards
are technically equivalent. However they are not fully comparable because of
the difference in testing speeds. The modulus determination requires a high
accuracy of ± 1 micrometer for the diameter.
Flexural tests—3-points
flexural tests are among the most common and classic methods for semi rigid and
rigid plastics.
Pendulum impact tests—impact tests are used to measure the behavior of materials at higher
deformation speeds. Pendulum impact testers are used to determine the energy
required to break a standardized specimen by measuring the height to which the
pendulum hammer rises after impacting the test piece.
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