Cross-linked polyethylene, commonly abbreviated PEX, XPE or XLPE, is a form of polyethylene with cross-links. It is used predominantly in building services pipework systems, hydronic radiant heating and cooling systems, domestic water piping, insulation for high tension (high voltage or high volt in short) electrical cables, and baby play mats. It is also used for natural gas and offshore oil applications, chemical transportation, and transportation of sewage and slurries. PEX is an alternative to polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC) or copper tubing for use as residential water pipes.
Properties Low-temperature impact strength, abrasion resistance and environmental stress cracking resistance can be increased significantly by crosslinking, whereas hardness and rigidity are somewhat reduced. Compared to thermoplastic polyethylene, PEX does not melt (analogous to elastomers) and is thermally resistant (over longer periods of up to 120 °C, for short periods without electrical or mechanical load up to 250 °C). With increasing crosslinking density also the maximum shear modulus increases (even at higher temperatures). Vorschau auf kunststoffe.de
Almost all PEX used for pipe and tubing is made from high-density polyethylene (HDPE). PEX contains cross-linked bonds in the polymer structure, changing the thermoplastic to a thermoset. Cross-linking is accomplished during or after the extrusion of the tubing. The required degree of cross-linking, according to ASTM Standard F876, is between 65% and 89%. A higher degree of cross-linking could result in brittleness and stress cracking of the material, while a lower degree of cross-linking could result in product with poorer physical properties.
PEX has significantly enhanced properties compared to ordinary PE. This is due to the introduction of crosslinks in the system, which can significantly improve the chemical, thermal, and mechanical properties of the polymer. While HDPE and PEX both display increases in the initial tangent modulus and yield stress under temperature or strain-rate increases when undergoing compression, HDPE tends to exhibit flow behavior after reaching a higher yield stress and PEX tends to exhibit strain-hardening after reaching its slightly lower yield stress. The latter exhibits some flow behavior but only after reaching higher true strains. The behavior observed in PEX is also mimicked by the thermoplastic ultra-high molecular weight polyethylene (UHMWPE). However, PEX displays a stronger temperature and strain-rate dependence than UHMWPE. Additionally, PEX is notable for its high thermal stability. It displays improved creep behavior (i.e. resists creep deformation) and maintains high strength and hardness at very high temperatures compared to thermoplastic polyethylene.
The type of initial polymer structure and amount of crosslinking can have a large impact on the resulting mechanical properties of PEX. Increased cross-linking is associated with higher Young's modulus and higher tensile strength though there is less elongation at the breaking point of PEX relative to HDPE.
Almost all cross-linkable polyethylene compounds (XLPE) for wire and cable applications are based on LDPE. XLPE-insulated cables have a rated maximum conductor temperature of 90 °C and an emergency rating up to 140 °C, depending on the standard used. They have a conductor short-circuit rating of 250 °C. XLPE has excellent dielectric properties, making it useful for medium voltage—1 to 69 kV AC, and high-voltage cables—up to 380 kV AC-voltage, and several hundred kV DC.
Preparation methods Various methods can be used to prepare PEX from thermoplastic polyethylene (PE-LD, PE-LLD or PE-HD). The first PEX material was prepared in the 1930s, by irradiating the extruded tube with an electron beam. The electron beam processing method was made feasible in the 1970s, but was still expensive. In the 1960s, Engel cross-linking was developed. In this method, a peroxide is mixed with the HDPE before extruding. In 1968, the Sioplas process using silicon hydride (silane) was patented, followed by another silane-based process, Monosil, in 1974. A process using vinylsilane followed in 1986.
Types of crosslinking A basic distinction is made between peroxide crosslinking (PE-Xa), silane crosslinking (PE-Xb), electron beam crosslinking (PE-Xc) and azo crosslinking (PE-Xd).
Shown are the peroxide, the silane and irradiation crosslinking. In each method, a hydrogen atom is removed from the polyethylene chain (top center), either by radiation or by peroxides (R-O-O-R), forming a radical. Then, two radical chains can crosslink, either directly (bottom left) or indirectly via silane compounds (bottom right).
Peroxide crosslinking (PE-Xa): The crosslinking of polyethylene using peroxides (e.g. dicumyl peroxide or di-tert-butyl peroxide) is still of major importance. In the so-called Engel process, a mixture of HDPE and 2% peroxide is at first mixed at low temperatures in an extruder and then crosslinked at high temperatures (between 200 °C and 250 °C). The peroxide decomposes to peroxide radicals (RO•), which abstract (remove) hydrogen atoms from the polymer chain, leading to radicals. When these combine, a crosslinked network is formed. The resulting polymer network is uniform, of low tension and high flexibility, whereby it is softer and tougher than (the irradiated) PE-Xc. The same process is used for LDPE as well, though the temperature may vary from 160 °C to 220 °C. Silane crosslinking (PE-Xb): In the presence of silanes (e.g. trimethoxyvinylsilane) polyethylene can initially be Si-functionalized by irradiation or by a small amount of a peroxide. Later Si-OH groups can be formed in a water bath by hydrolysis, which condense then and crosslink the PE by the formation of Si-O-Si bridges. Catalysts such as dibutyltin dilaurate may accelerate the reaction. Irradiation crosslinking (PE-Xc): The crosslinking of polyethylene is also possible by a downstream radiation source (usually an electron accelerator, occasionally an isotopic radiator). PE products are crosslinked below the crystalline melting point by splitting off hydrogen atoms. β-radiation possesses a penetration depth of 10 mm, ɣ-radiation 100 mm. Thereby the interior or specific areas can be excluded from the crosslinking. However, due to high capital and operating costs, radiation crosslinking plays only a minor role compared with the peroxide crosslinking. In contrast to peroxide crosslinking, the process is carried out in the solid state. Thereby, the cross-linking takes place primarily in the amorphous regions, while the crystallinity remains largely intact. Azo crosslinking (PE-Xd): In the so-called Lubonyl process polyethylene is crosslinked preadded azo compounds after extrusion in a hot salt bath.
Degree of crosslinking A low degree of crosslinking leads initially only to a multiplication of the molecular weight. The individual macromolecules are not linked and no covalent network is formed yet. Polyethylene that consists of those large molecules behaves similar to polyethylene of ultra high molecular weight (PE-UHMW), i.e. like a thermoplastic elastomer.
Upon further crosslinking (crosslinking degree about 80%),Günter Neroth, Dieter Vollenschaar: Wendehorst Baustoffkunde: Grundlagen – Baustoffe – Oberflächenschutz. 27. Auflage. Vieweg+Teubner Verlag/Springer Fachmedien, Wiesbaden 2011, , p. 931 the individual macromolecules are eventually connected to a network. This crosslinked polyethylene (PE-X) is chemically seen a thermoset, it shows above the melting point rubber-elastic behavior and cannot be processed in the melt anymore.
The degree of crosslinking (and hence the extent of the change) is different in intensity depending on the process. According to DIN 16892 (a quality requirement for pipes made of PE-X) at least the following degree of crosslinking must be achieved:
in peroxide crosslinking (PE-Xa): 75% with silane crosslinking (PE-Xb): 65% with electron beam crosslinking (PE-Xc): 60% in azo crosslinking (PE-Xd): 60%
Classification
North America All PEX pipe is manufactured with its design specifications listed directly on the pipe. These specifications are listed to explain the pipe's many standards as well as giving specific detailing about the manufacturer. The reason that all these specifications are given, are so that the installer is aware if the product is meeting standards for the necessary local codes. The labeling ensures the user that the tubing is up to all the standards listed.
Materials used in PEX pipes in North America are defined by cell classifications that are described in ASTM standards, the most common being ASTM F876. Cell classifications for PEX include 0006, 0008, 1006, 1008, 3006, 3008, 5006 and 5008, the most common being 5006. Classifications 0306, 3306, 5206 and 5306 are also common, these materials containing ultraviolet blockers and/or inhibitors for limited UV resistance. In North America all PEX tubing products are manufactured to ASTM, NSF and CSA product standards, among them the aforementioned ASTM standard F876 as well as F877, NSF International standards NSF 14 and NSF 61 ("NSF-pw"), and Canadian Standards Association standard B137.5, to which the pipes are tested, certified and listed. The listings and certifications met by each product appear on the printline of the pipe or tubing to ensure the product is used in the proper applications for which it was designed.
Europe In European standards. there are three classifications referred to as PEX-A, -B, and -C. The classes are not related to any type of rating system.
PEX-A (PE-Xa, PEXa) PEX-A is produced by the peroxide (Engel) method. This method performs "hot" cross-linking, above the crystal melting point. However, the process takes slightly longer than the other two methods as the polymer has to be kept at high temperature and pressure for long periods during the extrusion process. The cross-linked bonds are between carbon atoms.
PEX-B (PE-Xb, PEXb) The silane method, also called the "moisture cure" method, results in PEX-B. In this method, cross-linking is performed in a secondary post-extrusion process, producing cross-links between a cross-linking agent. The process is accelerated with heat and moisture. The cross-linked bonds are formed through silanol condensation between two grafted vinyltrimethoxysilane (VTMS) units, connecting the polyethylene chains with C-C-Si-O-Si-C-C bridges.
PEX-C (PE-Xc, PEXc) PEX-C is produced through electron beam processing, in a "cold" cross-linking process (below the crystal melting point). It provides less uniform, lower-degree cross-linking than the Engel method, especially at tube diameters over one inch (2.5 cm). When the process is not controlled properly, the outer layer of the tube may become brittle. However, it is the cleanest, most environmentally friendly method of the three, since it does not involve other chemicals and uses only high-energy electrons to split the carbon-hydrogen bonds and facilitate cross-linking.
Plumbing
PEX tubing is widely used to replace copper in plumbing applications. One estimate from 2006 was that residential use of PEX for delivering drinking water to home faucets was increasing by 40% annually. In 2006, The Philadelphia Inquirer recommended that plumbing installers switch from copper pipes to PEX.