Thermoplastic elastomer

Thermoplastic elastomers (TPE), sometimes referred to as thermoplastic rubbers, are a class of copolymers or a physical mix
of polymers (usually a plastic and a rubber) that consist of materials with both thermoplastic and elastomeric properties. While
most elastomers are thermosets, thermoplastics are in contrast relatively easy to use in manufacturing, for example, by injection
molding. Thermoplastic elastomers show advantages typical of both rubbery materials and plastic materials. The benefit of using
thermoplastic elastomers is the ability to stretch to moderate elongations and return to its near original shape creating a longer life
and better physical range than other materials.[1] The principal difference between thermoset elastomers and thermoplastic
elastomers is the type of cross-linking bond in their structures. In fact, crosslinking is a critical structural factor which imparts
high elastic properties.

IUPAC definition
Contents Thermoplastic elastomer:
Elastomer comprising a
Types thermoreversible network.[2]
Background
Advantages
Processing
Applications
References
Further reading

Types
There are six generic classes of commercial TPEs (designations acc. to ISO
18064):

Styrenic block copolymers, TPS (TPE-s)

Thermoplastic polyolefinelastomers, TPO (TPE-o)
Thermoplastic Vulcanizates, TPV (TPE-v or TPV)
Thermoplastic polyurethanes, TPU (TPU)
Thermoplastic copolyester, TPC (TPE-E)
Thermoplastic polyamides, TPA (TPE-A)
Thermoplastic polyurethanes
Not classified thermoplastic elastomers, TPZ
Examples of TPE materials that come from block copolymers group are amongst
others CAWITON, THERMOLAST K, THERMOLAST M, Arnitel, Hytrel, Dryflex, Mediprene, Kraton, Pibiflex, Sofprene, and
Laprene. Out of these styrenic block copolymers (TPE-s) are CAWITON, THERMOLAST K, THERMOLAST M, Sofprene,
Dryflex and Laprene. Desmopan or Elastollan are examples of thermoplastic polyurethanes (TPU). Santoprene, Termoton,
Solprene, THERMOLAST V, Vegaprene,[3] or Forprene are examples of TPV materials. Examples of thermoplastic olefin
elastomers (TPO) compound are For-Tec E or Engage. Ninjaflex used for 3D printing.

In order to qualify as a thermoplastic elastomer, a material must have these three essential characteristics:

The ability to be stretched to moderate elongations and, upon the removal of stress, return to something close to
its original shape
Processable as a melt at elevated temperature
 Absence of significant creep

Background
It was not until the 1950s, when thermoplastic polyurethane polymers became
available, that TPE became a commercial reality. During the 1960s styrene block
copolymer became available, and in the 1970s a wide range of TPEs came on the
scene. The worldwide usage of TPEs (680,000 tons/year in 1990) is growing at
about nine percent per year. The styrene-butadiene materials possess a two-phase
microstructure due to incompatibility between the polystyrene and polybutadiene
blocks, the former separating into spheres or rods depending on the exact
composition. With low polystyrene content, the material is elastomeric with the
properties of the polybutadiene predominating. Generally they offer a much
wider range of properties than conventional cross-linked rubbers because the
composition can vary to suit final construction goals. SBS block copolymer schematic
microstructure
Block copolymers are interesting because they can "microphase separate" to
form periodic nanostructures, as in the styrene-butadiene-styrene (SBS) block
copolymer shown at right. The polymer is known as Kraton and is used for shoe
soles and adhesives. Owing to the microfine structure, a transmission electron
microscope (TEM) was needed to examine the structure. The butadiene matrix
was stained with osmium tetroxide to provide contrast in the image. The material
was made by living polymerization so that the blocks are almost monodisperse,
so helping to create a very regular microstructure. The molecular weight of the
polystyrene blocks in the main picture is 102,000; the inset picture has a
molecular weight of 91,000, producing slightly smaller domains. The spacing
between domains has been confirmed by small-angle X-ray scattering, a SBS block copolymer in TEM
technique which gives information about microstructure. Since most polymers
are incompatible with one another, forming a block polymer will usually result
in phase separation, and the principle has been widely exploited since the introduction of the SBS block polymers, especially
where one of the block is highly crystalline. One exception to the rule of incompatibility is the material Noryl, where polystyrene
and polyphenylene oxide or PPO form a continuous blend with one another.

Other TPEs have crystalline domains where one kind of block co-crystallizes with other
block in adjacent chains, such as in copolyester rubbers, achieving the same effect as in
the SBS block polymers. Depending on the block length, the domains are generally more
stable than the latter owing to the higher crystal melting point. That point determines the
processing temperatures needed to shape the material, as well as the ultimate service use
temperatures of the product. Such materials include Hytrel, a polyester-polyether
copolymer and Pebax, a nylon or polyamide-polyether copolymer.

Advantages
TPE materials have the potential to be recyclable since they can be molded, extruded and Schematic crystalline block
copolymer
reused like plastics, but they have typical elastic properties of rubbers which are not
recyclable owing to their thermosetting characteristics. They can also be ground up and
turned into 3D printing filament with a recyclebot. TPE also require little or no compounding, with no need to add reinforcing
agents, stabilizers or cure systems. Hence, batch-to-batch variations in weighting and metering components are absent, leading to
improved consistency in both raw materials and fabricated articles. Depending on the environment, TPEs have outstanding
thermal properties and material stability when exposed to a broad range of temperatures and non-polar materials.[1] TPEs
consume less energy to produce, can be colored easily by most dyes, and allow economical quality control.

Processing
The two most important manufacturing methods with TPEs are extrusion and injection molding. TPEs can now be 3D printed and
have been shown to be economically advantageous to make products using distributed manufacturing.[4][5] Compression molding
is seldom, if ever, used. Fabrication via injection molding is extremely rapid and highly economical. Both the equipment and
methods normally used for the extrusion or injection molding of a conventional thermoplastic are generally suitable for TPEs.
TPEs can also be processed by blow molding, melt calendaring,[6] thermoforming, and heat welding.

Applications
TPEs are used where conventional elastomers cannot provide the range of physical properties needed in the product. These
materials find large application in the automotive sector and in household appliances sector. In 2014 the world market for TPEs
reached a volume of ca. 16.7 billion US dollars. About 40% of all TPE products are used in the manufacturing of vehicles.[7] For
instance copolyester TPEs are used in snowmobile tracks where stiffness and abrasion resistance are at a premium. Thermoplastic
olefins (TPO) are increasingly used as a roofing material[8]. TPEs are also widely used for catheters where nylon block
copolymers offer a range of softness ideal for patients. Thermoplastic silicone and olefin blends are used for extrusion of glass
run and dynamic weatherstripping car profiles. Styrene block copolymers are used in shoe soles for their ease of processing, and
widely as adhesives. Owing to their unrivaled abilities in two-component injection molding to various thermoplastic substrates,
engineered TPS materials also cover a broad range of technical applications ranging from automotive market to consumer and
medical products. Examples of those are soft grip surfaces, design elements, back-lit switches and surfaces, as well as sealings,
gaskets, or damping elements. TPE is commonly used to make suspension bushings for automotive performance applications
because of its greater resistance to deformation when compared to regular rubber bushings. Thermoplastics have experienced
growth in the heating, ventilation, and air conditioning (HVAC) industry due to the function, cost effectiveness and adaptability to
modify plastic resins into a variety of covers, fans and housings. TPE may also be used in medical devices and is also finding
more and more uses as an electrical cable jacket and inner insulation. You'll also be able to find TPE used in sex toys and some
headphone cables.

References
1. Levensalor, Alex. "The Benefits of Hytrel in Modern Belting" (http://industrial.beltcorp.com/blog/the-benefits-of-hyt
rel-in-modern-belting). Retrieved 2016-10-27.
2. Alemán, J. V.; Chadwick, A. V.; He, J.; Hess, M.; Horie, K.; Jones, R. G.; Kratochvíl, P.; Meisel, I.; Mita, I.; Moad,
G.; Penczek, S.; Stepto, R. F. T. (1 January 2007). "Definitions of terms relating to the structure and processing of
sols, gels, networks, and inorganic-organic hybrid materials (IUPAC Recommendations 2007)". Pure and Applied
Chemistry. 79 (10): 1801–1829. doi:10.1351/pac200779101801 (https://doi.org/10.1351%2Fpac200779101801).
3. "Innovation in materials" (http://www.hutchinson.com/en/innovation-materials). www.hutchinson.com. Retrieved
2017-02-27.
4. Woern, Aubrey L.; Pearce, Joshua M. (2017-10-30). "Distributed Manufacturing of Flexible Products: Technical
Feasibility and Economic Viability". Technologies. 5 (4): 71. doi:10.3390/technologies5040071 (https://doi.org/10.
3390%2Ftechnologies5040071).
5. "Is Flexible 3D Printer Filament Worth the Investment? | 3DPrint.com | The Voice of 3D Printing / Additive
Manufacturing" (https://3dprint.com/192599/flexible-3d-printer-filament/). 3dprint.com. 2017-10-30. Retrieved
2018-03-10.
6. "Processing methods for thermoplastic elastomers-TPE - Introduction" (https://www.tut.fi/ms/muo/vert/8_processi
ng/5.1.htm). www.tut.fi. Retrieved 2016-10-27.
 7. Kuehner, Marcel. "Thermoplastic Elastomers (TPE) - Market Study - Ceresana" (http://www.ceresana.com/en/ma
rket-studies/plastics/thermoplastic-elastomers/). www.ceresana.com.
8. "ASTM D6878 / D6878M - 17 Standard Specification for Thermoplastic Polyolefin Based Sheet Roofing" (https://
www.astm.org/Standards/D6878.htm). www.astm.org. Retrieved 2018-03-18.

Further reading
PR Lewis and C Price, Polymer, 13, 20 (1972)
Modern Plastic Mid-October Encyclopedia Issue, Introduction to TPEs, page:109-110

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