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Prepared by Lewis A. Parks, Ph.D. Sterigenics Advanced Applications February 2, 2010
Crosslinking (or cross-linking, cross linking) is a process where the long chains of polymers are linked together increasing the molecular mass of the polymer as a result. Properties of polymer products that can be improved by crosslinking include: Mechanical properties, such as tensile strength Scratch resistance Performance at higher temperatures, often with an increase in the melting temperature Resistance to chemicals because of lowered solubility in organic solvent Gas permeation reduction Shape memory retention. Elastomers may be crosslinked to a slight degree to give them “memory” – they will return to their original shape after being expanded.
Depending upon the polymer, different techniques may be used to cause crosslinking. In all cases, the chemical structure of the polymer is altered through the crosslinking process. This can be done by adding different chemicals in conjunction with heating and, sometimes, pressure. One of the earliest examples of crosslinking is the vulcanization of natural rubber by adding sulfur under heat, which creates the links between the latex molecules. Vulcanization gives the rubber its strength properties over temperature ranges in which non-vulcanized rubber could not perform. Alternatively, the polymer may be crosslinked using high-energy ionizing radiation, ie electron beam (or e-beam, e beam), gamma, or x-ray. Gamma irradiation is usually most economical at lower doses (~80 kGy and below) and for large, high density parts. Electron beam is commonly used for small parts, particularly low density parts, and linear product processed reel to reel (eg, wire, cable, tubing). Irradiation creates free radicals which will often chemically react in various ways, sometimes at slow reaction rates. The free radicals can recombine forming the crosslinks. The degree of crosslinking depends upon the polymer and radiation dose. One of the benefits of using irradiation for crosslinking is that the degree of crosslinking can be easily controlled by the amount of dose. Other subtle influences include the
The table lists their G values for crosslinking (GX) and scissioning (GS). This oxidation process may reduced by antioxidants added to the polymer resin. depending upon the polymer and the dose. polyethylene will release hydrogen during irradiation. occurs when polymers are irradiated. For example. These can be converted to units of μmol J-1 by multiplying G by 0. . depending upon the polymer. These data are from several sources. When evaluating a polymer to irradiate. usually at relatively insignificant amounts. Table 1 lists polymers which are radiation crosslinkable. p 351).additives in the base polymer and the type of radiation used (related to the dose rate). Furthermore. Another influence which may not be as subtle is oxidation during irradiation. This effect will be more predominant when using gamma irradiation as compared to the much faster electron beam irradiation process. overlooking the subtle influences. a low GX value would indicate a need for higher doses to achieve property improvements. the polymer chains are broken and molecular mass decreases. interaction of the polymer or the gas with ozone created during the irradiation of the neighboring air may need to be considered. oxidation can continue after irradiation cuasing changes in properties with time. Another byproduct which can be created. called scissioning. and listed ranges can arise from the different brands of polymers studied within a polymer family. Although some polymers may crosslink at a greater rate than scission. defined as the number of events that occurs with the absorption of 100 eV of energy. In this case.1036 (Ref 1. is gas emission. The rate of occurrence for these two processes is the G value. A competing process. Scissioning and crosslinking occur at the same time where one may predominate over the other.
76 (3) 0. 10 0.01 – 0.25 (1) 0.85 (3) 1.67 (3) 0.62 (3) 0.5 (1) For Polyethylene GS / GX High density polyethylene Ethylene – propylene copolymer Polyvinyl acetate 2.68 (3) 0.6 – 1.5 (1) Irradiated in O2 (2) ~0.3 – 1.7 – 1.6 Nylon 6.38 (1) (1) Depends on composition of copolymer 0.1 – 0.07 Irradiated in O2 (2) 0.5 (1) 0.3 0.5 – 1.1 (1) GS Irradiated in vacuo 0.03 – 0.Table 1 Selected radiation crosslinkable polymers GX Polymer Low density polyethylene Linear low density polyethylene Irradiated in air 0.02 (1) 0.4 – 0.15 (1) 0.4 (1) 0.4 – 1.18 Purified rubber irradiated in vacuum (2) Polyvinyl chloride Polystyrene Natural rubber Polyamides (see also Table 2) Nylon 6 Nylon 6.1 0.10 (3) .3 – 2.85 (3) 0.05 (1) 1.12 (3) 0.3 – 1.10 Nylon 11 Nylon 12 Nylon 10.02 – 0.92 (3) 0.8 – 1.70 (3) 0.3 (1) 0.92 (3) 1.50 (3) 0.25 (1) 0.
4) Polybutadienestyrene (SBR. antirads can be added to reduce the degree of radiation crosslinking. The primary gases released during irradiation of polypropylene under vacuum are hydrogen and . 85% styrene) Ethylene-propylenediene-monomer (EPDM. Scission and crosslinking both occur in nearly the same amounts when polypropylene is irradiated. which can further result in reducing potential adverse effects. free radical generation. and gas evolution.26 (2) GX of the polymers listed in Table 1 can generally be enhanced through the addition of crosslinking promoters. p 351. called prorads. 16% styrene) Polybutadienestyrene (SBR.9 (2) 0. with this effect much more pronounced using gamma irradiation compared to electron beam (Ref 4). p 564). 355 – and references therein (2) Ref 2. Although not as common. atactic / syndiotactic) (Ref 2. such as oxidation. antioxidants are added to make polypropylene parts radiation sterilizable. This enhanced crosslinking behavior is also seen for amorphous polyethylene and some other polymers compared to their semi-crystalline species Polypropylene has a high rate of oxidation during and after irradiation.Nylon 12. This can reduce the dose needed for crosslinking.14 (3) 0.3 (2) 2.1 (2) 2.07 (3) 0.0 mole% EN) 1. 57 mole% ethylene + 2. 574 (3) Ref 3 0.07 (3) 5.18 (2) (1) Ref 1.3 (2) 1. 10 Nylon MPD 10 Polybutadiene (cis1.10 (3) 0. with purely amorphous polymer (atactic) crosslinking at higher rates than semi-crystalline polymer (atactic / isotactic. p 563. For this reason. The use of prorads provides opportunities to create radiation crosslinked products from base polymer materials which could not otherwise be created.
along with Table 1. radiation crosslinking of polypropylene is an unlikely candidate for property improvements. There are many other niche products that are manufactured using crosslinking. Because of scissioning and. This table. oxidation that occur. . such as those listed in Table 1. Notable products that are made using radiation crosslinking are listed in Table 2. more importantly.methane. should be used as a catalyst to realize other potential applications using radiation crosslinkable materials. When irradiated in air. carbon dioxide and carbon monoxide are also produced.
aircraft. Wire and cable insulation Improved mechanical strength and insulation properties. . particularly for high temperature applications. Improved mechanical and burst strength for higher temperature plumbing and water transport pipe. polyamide *.) Film: Lower gas permeability and better performance at low temperatures compared to non-irradiated films. ships and other markets.. Additives are important (antioxidants. eg self-regulating heaters Improved temperature resistance Improved resistance to chemicals No contamination from chemical crosslinkers Simultaneous sterilization is possible Crosslinking promoters added Primarily to increase temperature resistivity Automotive underhood and other applications Crosslinking during the foaming process to increase melt viscosity resulting in lower density closed cell foam.Table 2. Notable products made using radiation crosslinking. Radiation pretreatment of tire components to allow blending of synthetic rubber and to reduce energy costs compared to thermal methods Extruded polysiloxane gaskets and tubes Polysiloxane electrical insulation tape Polysiloxane rubber based / fabric Heat shrinkable products Polymeric Positive Temperature Coefficient Products Gaskets and seals Hydrogels Products from radiation crosslinked engineering plastic (eg polybutylenterephthalate.) Polyolefin foams PEX-c pipe Vulcanization . prorads.. etc. flame retardants. Used in automobiles. trains. Tubing Resettable fuses Heat tracing products.
Their benefits and disadvantages are listed in Tables 4 and 5 and can be contrasted to the benefits and disadvantages of using radiation crosslinking. When needed. Benefits and disadvantages of silane crosslinking (Ref 5) Benefits Low initial investment for in-house crosslinking Broadly known Easily understandable technique Small batches may be processed Disadvantages Limited to few number of polymers Relatively complicated compound design Limited storage life of compounds Controlling the crosslinking is sensitive “Dirtier” process with the potential for undesirable residuals in the product .pts-marketing. PTS Plastic Technology Service. Also suppliers of radiation crosslinkable polyester elastomer and other elastomers.frisetta-polymer. listed in Table 3.de. Table 3. Benefits and disadvantages of radiation crosslinking Benefits Many polymers can be crosslinked. compounds often relatively simpler A number of service centers can offer radiation crosslinking services worldwide Versatile technology: Degree of crosslinking can be controlled with the dose and small batches may be processed Crosslinked products can be developed with postponement of capital investment after market acceptance of the new product using a service center Reliable Efficient use of energy “Cleaner” process with the potential for no unwanted residuals in the product Disadvantages Benefits and process of radiation crosslinking not widely understood Use of a service center means product must be shipped and placed in the control of others during the irradiation process High capital cost and equipment expertise is needed for in-house crosslinking Table 4.* Suppliers of radiation crosslinkable polyamide (enhanced with prorads) are: Frisetta Polymer.de/. http://www. www. Two common chemical crosslinking techniques are silane and peroxide crosslinking.
Phys. Ishigaki and F. Edward Phillips. resins of materials listed in Table 1 may be irradiated at doses lower than those used for crosslinking to create long chain branching. 5 Ron Goethals. 39. Yoshii. M. Examples are irradiated polyethylenes (Ref 6. Chem. gamma ray. 2 K. and Lewis Parks. Benefits and disadvantages of peroxide crosslinking (Ref 5) Benefits Reasonable initial investment for in-house crosslinking An easily understandable technique Reasonable range of polymers can be crosslinked with this technique. Makaucchi. Radiat. 1996). radiation crosslinking. although not as widely used as chemical crosslinking. C. Chem. radiation crosslinking is usually performed in service centers located around the world. United States Patent US 7. James E. 527 (1992). polymers. 3 K. Physical Properties of Polymers Handbook. Glover. Pikaev. p 564).472 B2. NY. 4 I. Applied Radiation Chemistry: Radiation Processing. Because of the high capital cost of radiation processing equipment. ed. Abe. Phys. offers several advantages over chemical crosslinking. Inc. In fact. 7 Radiation Treated Ethylene Polymers and Articles Made From Said Polymers. Dϋsseldorf. 563 (2009). Woods and Alexei K. 78. Radiat. presentation at Crosslinking Polyolefins 2005. Woodbury. x ray References: 1 Robert J. New York 1994). irradiation. prorad. and T. compare to silane technique Reliable Disadvantages Relatively complicated compound design High energy consumption Heat and pressure can affect components internal to material being crosslinked One of the advantages of radiation crosslinking is that the amount of crosslinking can be controlled by the amount of dose used. This influences the melt flow properties of the materials by decreasing their melt flow index and enhancing melt strength during processing. 6 Song Cheng. a precursor to crosslinking. (John Wiley & Sons. peroxide crosslinking.Table 5. 7) used in products such as films (Ref 8) and foams (Ref 9) which can benefit from enhanced melt strength during manufacture. Dawes and L. radiation crosslinking.094. Reference Data: crosslinking (aka cross-linking and cross linking). 686 (1976). . Mark (American Institute of Physics Press. vulcanization.. and ethylene vinyl acetate (Ref 3. electron beam (aka e-beam and e beam). In summary. Nippon Kagaku Kaishi. Asano. silane crosslinking.
United States Patent US 4.525. United States Patent US 6. .386 B1. 9 Compitable Linear and Branched Ethylenic Polymers and Foam Therefrom.593.257 (1985).8 Low Level Irradiated Linear Low Density Ethylene / Alpha-Olefin Copolymers and Film Extruded Therefrom.
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