High Energy Radiation and Polymers, A Review of Commercial Processes and Emerging Applications

Nuclear Instruments and Methods in Physics Research B 185 (2001) 833
www.elsevier.com/locate/nimb
High-energy radiation and polymers: A review of commercial processes and emerging applications
R.L. Clough
*
Organic Materials Department, Sandia National Laboratories, M.S. 0888, Albuquerque, NM 87185-0888, USA
Abstract Ionizing radiation has been found to be widely applicable in modifying the structure and properties of polymers, and can be used to tailor the performance of either bulk materials or surfaces. Fifty years of research in polymer radiation chemistry has led to numerous applications of commercial and economic importance, and work remains active in the application of radiation to practical uses involving polymeric materials. This paper provides a survey of radiationprocessing methods of industrial interest, ranging from technologies already commercially well established, through innovations in the active R&D stage which show exceptional promise for future commercial use. Radiation-processing technologies are discussed under the following categories: cross-linking of plastics and rubbers, curing of coatings and inks, heat-shrink products, bermatrix composites, chain-scission for processing control, surface modication, grafting, hydrogels, sterilization, natural product enhancement, plastics recycling, ceramic precursors, electronic property materials, ion-track membranes and lithography for microdevice production. In addition to new technological innovations utilizing conventional gamma and e-beam sources, a number of promising new applications make use of novel radiation types which include ion beams (heavy ions, light ions, highly focused microscopic beams and highintensity pulses), soft X-rays which are focused, coherent X-rays (from a synchrotron) and e-beams which undergo scattering to generate patterns. Published by Elsevier Science B.V.
1. Introduction and overview It has been approximately 50 years since researchers rst began exposing polymeric materials to ionizing radiation, and reporting the occurrence of cross-linking and other useful eects. Today, a substantial commercial industry is in place based on processing of polymers with radiation. Innovation in this eld has by no means ended; im-
Tel.: +1-505-844-3492; fax: +1-505-844-9624. E-mail address: rlcloug@sandia.gov (R.L. Clough).
portant new products made possible through radiation technology continue to enter the marketplace, and exciting new innovations in the application of radiation to macromolecular materials are under exploration at research institutions around the world. In this paper we review both the successful radiation processing technologies now in use, and new polymer radiation technologies that are emerging from research laboratories. The radiation technologies being applied to polymer processing comprise a diverse set, with many dierent radiation types and sources used, many dierent types and combinations of materials, and
0168-583X/01/$ - see front matter Published by Elsevier Science B.V. PII: S 0 1 6 8 - 5 8 3 X ( 0 1 ) 0 0 9 6 6 - 1
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833
many dierent application objectives being addressed [114]. Specialists in the polymer radiation chemistry eld are typically focused on a limited number of these technologies. An objective of this paper is to provide these workers, and polymer scientists in general, with an overview on the status of progress toward commercial products and technologies in the broad area of radiation processing. Cross-linking by radiation, a relatively mature technology, encompasses many product applications of signicant economic impact. Particularly large are the industries utilizing radiation for producing cross-linked wire insulation, and also for heat-shrink products such as food wrap and tubing for electrical connections. More recently, large-volume industrial production of self-resetting polymer-based electrical fuses and self-regulating heat tape has arisen, using technology closely related to the heat-shrink products. Curing of coatings and inks is also an established, economically important industry, and many other cross-linking applications have been successfully commercialized, as in the production of tubing, pipes and automobile tires. More recently, radiation curing of bermatrix composites has begun to come into use. The opposite of cross-linking chain scission is the basis of other radiation treatments aimed at enhancing processing characteristics of polymers. A large commercial industry exists in the irradiation of Teon, which reduces particle size and molecular weight, and allows incorporation of the material into coatings, inks, etc. Alteration of the molecular weight distribution of polypropylene (PP) to enhance melt ow characteristics and to allow alternative means of molding is a growing commercial process. Radiation sterilization of disposable plastic medical items (syringes, tubing, vials, gauze, etc.) has captured a large and still growing segment of the market in many industrialized countries, due to advantages such as elimination of toxic residues which are problematic in chemical sterilization. As with a number of other radiation-processing technologies, control of unwanted material changes, including post-irradiation degradation in mechanical properties and discoloration, has been an integral part of commercialization, and is still an
active area for example in the radiation sterilization of UHMWPE materials used for hip joint replacement, long-term stability remains an issue. Two of the most active research areas for radiation processing in the past 56 years, as reected by the number of papers published, are grafting and hydrogels. Both have important biomedical applications. Hydrogels (cross-linked and sterilized by irradiation) are now a successful and growing commercial product used for application to burns and wounds. Other emerging applications include contact lenses and superabsorbant materials. Stimuli-responsive hydrogels, which contract under the inuence of external factors such as temperature or pH, are under active investigation for a wide range of applications including regulated drug release. Grafting is being pursued in laboratories throughout the world because of the many applications which would be impacted by the ability to tailor surface properties of a material while it retains its bulk properties. Some of the surface characteristics being successfully manipulated by radiation grafting include: chemical resistance, wetability, biocompatibility (including antithrombogenic properties), dyeability of fabrics, and antistatic properties. Grafting of materials to render them capable of binding enzymes, proteins and similar species, has yielded products useful for carrying out chemical treatment of substrates and for chromatographic separation of biological materials. Grafting has also been used to produce ion exchange membranes for purposes such as removal of heavy metals from aqueous waste streams. The radiation treatment of low-value and/or waste agricultural byproducts based on naturally occurring polymers (including cellulose, starch, straw, peanut shells, and many others), in an eort to produce useful products (polymer llers, bers, absorbents, etc.), remains an active area of processing technology development. Surface modication and grafting of polymer chains, as well as modication of the bulk material, are employed in such treatments. The radiation treatment of consumer waste plastics, for purposes of recycling, is an emerging area of investigation motivated both by environmental and economic considerations.
10
Both the cross-linking of remolded (often blended) materials for enhanced strength, and in other cases degradation, are being pursued. New radiation processing applications involving ion-beam treatment of polymers oer exciting prospects for future commercialization, and are under active investigation in many research laboratories. Ions are well suited for surface alteration. They have a limited depth of penetration, which provides the potential for very ecient use of energy when surface treatment is the objective. They also allow for surface alteration without changing the properties of the underlying bulk materials. The use of ion beams has been shown to dramatically enhance the abrasion resistance of polymeric materials. In other studies, high-intensity ion pulses were used to create foam-like surface morphologies of interest for enhanced adhesion properties. The use of heavy ions in irradiating polymer surfaces and thin lms has been a particularly active area in recent years. One technology that is especially promising for commercial application is the chemical treatment of irradiated thin polymer lms to yield porous ion-track membranes. The pore surfaces can be altered by a grafting process to control the binding of specic species (such as proteins), and thereby produce selective ltration systems. By binding stimuli-responsive hydrogels into the pores, it is possible to create a membrane that can be opened and closed at will. One more processing technology having enormous commercial potential, which is currently in the laboratory stage, is radiation-based lithography for microelectronic circuit production. This technology, which operates by radiation-induced chemistry of a polymer-based patterning layer (the ``resist'' material), will allow production of smaller microcircuit sizes compared with conventional photolithography, which has reached a limit due to the wavelength of light being used. Two competing approaches utilize (1) an e-beam and (2) soft X-rays. One of these will likely become the dominant production process for commercial computer chips by the beginning of the next decade. Related to microelectronic applications is the use of X-ray radiation from a synchrotron (LIGA process), and of microscopic ion beams (DIBL), in
the manufacturing of ultra-small devices and micromachines. Other useful applications of radiation-treatment of polymers are under continuing investigation. These include the processing of ceramic precursors, and the development of electronicproperty materials. 2. Types of radiation facilities for commercial application At present, the two most common radiation types in industrial use are gamma and e-beam. The gamma facilities are mainly cobalt-60. Machi of IAEA reported [1] that there are about 200 such industrial gamma facilities worldwide. Their advantages include the fact that gamma rays are very penetrating. The technology is extremely simple, so there is low downtime for a gamma source. Also, it is not sensitive to electricity prices. Gamma sources are most heavily used today [15] for radiation sterilization of disposable plastic medical items. E-beam machines [16,17] play a signicant role in the processing of polymeric materials; a number of dierent machine designs and dierent energies are available. Industrial e-beam accelerators with energies in the 150300 keV range are in use in applications where low penetration is needed, such as curing of surface coatings. Accelerators operating in the 1.5 MeV range are used where more penetration is needed, as in the cross-linking of cable insulation. High-energy commercial ebeams, operating in the 10 MeV range, are used for applications such as sterilization of boxes lled with disposable medical devices [18]. Today, there are on the order of 1000 e-beam machines in industrial use worldwide [1]. E-beam machines have a high-dose rate and therefore short processing times. While they have limited penetration compared with gamma, they conversely have good utilization of energy because it can all be absorbed by the sample being irradiated. E-beams, of course, can be switched o when not in use. Because they contain no radioactive isotope, this provides an advantage from a public acceptance standpoint. Also, there is no radioactive source
11
material that must eventually be disposed of when the facility is decommissioned. Many of the e-beam and gamma radiation facilities that are used commercially today are captive; they are owned by a particular company and used exclusively on that company's specic product line. There are other facilities that service many customers or companies coming to them to purchase beam time, and they process a whole range of dierent materials. E-beam machines can also be used to generate X-rays, where more penetration is needed, although this conversion has relatively low eciency. Some specialized X-ray-producing devices are being utilized in developing radiation-processing applications with polymers, particularly in technologies involving lithographic production of microcircuits and micromachines. These include both plasma X-ray sources and synchrotrons. Ion beams are being used to create new technology in polymer processing. Whereas they have been extensively applied in commercial application for ion implantation in the production of semiconductor devices, and have also been applied for surface hardening of metals, they are just beginning to be adapted for commercial use with macromolecular materials. A great variety of dierent ion-beam machines are in existence, having widely varying energies, and operating in both continuous and pulsed mode. Ions are of most interest for treatment of polymer surfaces and thin lms because they have extremely low penetration depths. Many dierent ions have been employed for irradiating polymers, ranging from hydrogen and helium ions, up to ions of heavy elements such as gold or uranium. 3. Cross-linking of plastics and rubbers Cross-linking of polymer chains is the basis of the largest commercial applications involving radiation and polymers. This technology owed from initial observations by Charlesby [20] that polyethylene, when exposed to radiation emanating from a reactor, formed insoluble gel. Up until that time, cross-linking had been thought to be possible only through the addition of chemical
agents to polymers having suitable functional groups (i.e. double bonds); sulfur vulcanization of rubber was the primary example. The discovery that ionizing radiation could act upon the interior of bulk polymers, to eect the formation of covalent bonds between polymer chains in the absence of a chemical additive, and that this could even occur with polymers lacking reactive functional groups, was an astonishing concept at the time [19], which created excitement throughout the scientic community and served to launch the eld of polymer radiation chemistry [20]. Since that time, a large volume of literature has appeared, describing the cross-linking of a wide range of polymers by exposure to radiation, and this technology has been commercialized in countries throughout the world. Polymers that are cross-linked can maintain their shape and useful properties at a higher temperature i.e. they do not ow. Generally, crosslinked materials have better strength, and better resistance to impact and stress cracking. They have improved creep resistance and in many cases improved chemical resistance. Some of the advantages of radiation cross-linking compared to conventional cross-linking with chemical additives are cost, speed, the ability to cross-link preformed parts at or near room temperature, reduction of chemical ingredients and chemical residues for environmental or toxicological reasons, and, in many cases, superior material properties in the nal product. Literature reports continue to appear in recent years describing the radiation cross-linking of a variety of dierent rubber types, including such diverse materials as latex, silicone, styrenebutadiene block copolymers, EPDM, polybutyleneterephthalate, nitrile rubber, PMMA/ABN blends and others [2129]. In some cases, remarkable improvements in properties have been reported. For example, styrenebutadiene rubber tank track pads that were cured using both sulfur and an e-beam, were reported to have much better wear properties and superior ozone resistance compared with materials cured with sulfur alone [30]. Radiation cross-linking of polymeric foams is a commercial process, and reports continue to appear on cross-linking of foam for applications of
12
automotive cushions, heat insulation, buoyancy products for marine use, and sporting goods [31 33]. Numerous studies reporting benecial eects of various additives in promoting radiation crosslinking also continue to be published; these have included the widely used multifunctional acrylates [3436], and also acetylene gas [37]. A substantial fraction of cable insulation is cross-linked using radiation [38]. A large amount of PE-based insulation is produced in this way, as well as signicant quantities of insulation made of PVC and of partially uorinated polymers [39]. Radiation-cross-linked material is most extensively used in high-performance applications. About half of aircraft and aerospace cable is crosslinked by radiation, and the higher-stability wiring in automotive applications, which has to resist heat and solvents, also tends to be radiation cross-linked. Another common product in which radiation is used commercially by some major companies is automobile tires. Uncured rubber materials are given a moderate dose causing a low degree of cross-linking to provide ``green strength;'' this gives rubber parts the initial properties necessary for the tire building process. Irradiation can be very useful in the processing of polymer blends [40,41], which often undergo physical phase-separation of the components, due to incompatibility of the materials. In a number of blend systems, irradiation has been used to induce cross-linking of one or more of the components, and/or formation of cross-links between the different phases, resulting in improvement of physical properties [42,43]. Cross-linking can also be used for xation of a non-equilibrium blend morphology. The transient morphology of the blend can be selectively controlled during processing, based on temperature and shear stress. Then, e-beam irradiation of the physical blend, as it emerges from an extruder, can be used to ``lock in'' a particular desired morphology of one cross-linkable phase that is disbursed in a non-cross-linkable phase. When this material is used for subsequent molding, the non-cross-linked phase ows, while the cross-linked phase largely maintains its shape (brils, spheres, or other). This procedure allows signicant control over the properties of the nal material made from the blend [4447].
The IAEA has recently completed a large international program for perfecting and implementing the radiation cross-linking of natural latex in the production of rubber gloves and similar items. Advantages include the elimination of allergic reactions for wearers, and elimination of sulfur oxides (due to the conventional sulfur cure) during destruction of the medical wastes through burning. In Europe, radiation-cross-linked PE pipes are used extensively for carrying hot water utilized in heating of buildings. In Germany alone, 80 million meters of PE pipe are radiation cross-linked per year [48]. Other consumer products being crosslinked by radiation include: gaskets, bottles, lms, seals and tubing. It is well known that polymers can be divided into two types: those which predominantly crosslink when exposed to radiation, and those which undergo primarily chain scission. Tables classifying polymers into these two categories have been published [49]. Recent work has shown that at least one polymer which is inherently of the scissioning type (polytetrauoroethylene, PTFE), can be cross-linked by proper choice of irradiation conditions. This can be achieved by irradiation at elevated temperature under inert atmosphere, within a narrow range that is just above the melting point [5057]. This discovery will now allow a way of improving the abrasion resistance and other properties of ``teon'' materials. As a general comment, it should be noted that experimental and environmental conditions inuence the balance between radiation-induced cross-linking and scission reactions for most polymers: irradiation in the presence of air, particularly at low dose rates and with thin samples, can result in predominantly oxidative scission reactions [58], even for polymers of the cross-linking type. A nal example of radiation-induced crosslinking is the formation of polymeric spheres and particles having diameters in the micron and submicron range [5965]. This is accomplished by gamma or e-beam irradiation of an emulsion containing one or more monomers (often multifunctional). A variety of applications are possible for such materials, including chromatographic or catalytic supports, and latexes.
13
4. Curing of coatings and inks E-beam curing has come into extensive use in surface coating and printing, particularly for the graphic arts and packaging industries [6668]. Such coatings adhere well to a variety of surfaces, including paper, wood, glass, metals, plastics, and textiles. This industry continues growing at the rate of about 10% per year as of 1998 [69]. The word curing is often used to refer to the process of cross-linking and polymerizing oligomeric resins. For coating applications, which require very little depth of penetration, relatively low-energy self-shielded electron accelerators are employed [70]. E-beam curing is used in providing many commercial products [7180]. These include: coatings on wood for indoor and outdoor applications, scu-resistant oor coverings, adhesive layers on tape, printing inks, glossy varnish layers for graphic arts (such as magazine covers), barrier layers to gas transmission for laminates used in packaging, silicone ``release'' surfaces (such as backing on press-apply adhesive labels), antistatic layers, ber-optic coatings, information storage layers (for credit cards, audiotapes, etc.), and sealants to protect cement and other porous substrates. Resin chemistries include acrylates and vinyl ethers. A survey of the radiation curing industry performed in 1998 [69] identied the most extensive product categories for which radiation curing is used in processing coatings. These areas, in descending order of importance, are: overprint coatings, inks, wood nishes, coatings on plastics, silicone release materials, adhesives, and decorative coatings on metals. E-beam curing provides many positive features [66,71,81] including solvent-free systems, energy savings, high extent of cure, and high throughput rate of fully cured (dry) product. E-beams provide penetration of heavily pigmented coatings, and have the capability of curing an adhesive layer lying between two opaque layers. Radiation cured materials often show improved properties compared with thermally cured product. Disadvantages include the frequent necessity of providing an inert atmosphere over the surface undergoing cure in order to prevent inhibition of the curing chemistry by reaction with O2 , and high-initial
capital cost for the irradiation equipment. A recent study, which shows promise for ameliorating the rst of these problems, reported that inclusion of certain phosphite additives in the resin greatly reduced oxidative chemistries, and allowed some ebeam curing to be carried out in air [82]. Another successful approach has been the incorporation of additives (such as `ìodonium'' salts) which induce curing through an ionic mechanism that is insensitive to the presence of O2 [83]. Since very little depth of penetration is required, ultraviolet (UV) curing of resins in thin layers is also widely used in industry; similar resins and applications apply. Due to several reasons, including lower equipment costs, UV is presently more widely used in commercial coating applications than e-beams. 5. Heat shrink products Another interesting cross-linking-related technology is the ``memory eect'' which is the basis of the production of heat-shrink materials such as food wrap, tubing for electrical connections, and many other products. Polyethylene-based materials are primarily used in this application. The material is radiation cross-linked. It is then heated above the melting point of the crystalline regions that exist in the polymer, stretched (typically to a size about twice its original dimensions), and then cooled back down while in the stretched conformation. The material specimen retains its stretched size and shape until the next time it is heated, at which point the cross-links that were created in the sample's smaller, unstretched state, pull the material back into its original shape, causing it to shrink and mold to the object which it surrounds. For example, the technology is used in heat-shrink electrical connectors: heat shrink tubing can be put around spliced wires; it is heated, causing it to shrink very snugly around the spliced area. This technology, which comprises cross-linking at room temperature without melting of crystallites in the material, is uniquely suited to the use of ionizing radiation. It cannot be easily achieved with conventional chemical techniques, as these require heating of the material to induce cross-linking chemistry, with consequent melting of crystals;
14
upon cooling crystallinity is reduced. The production of heat-shrink products is the basis of a large industry, as typied by Raychem [84,85]; others have now developed this technology as well [8688]. Related technologies using this memory eect are now developing into high-volume products. Resettable polymeric fuses are a good example: a polymeric material, which contains carbon black ller inside to make a conductive pathway, is radiation cross-linked. When the material heats up because excess current is owing through it, the polymer expands and disrupts this carbon black conductive network, with the result that electrical conduction is stopped. As the material then cools, it shrinks back to its original shape and the fuse is reset. The cross-links serve to keep the material from owing when it is in its expanded (heated) state, and also help pull it back into position when it is cooled. A similar material is used to make a self-regulating heater. A carbon-black-lled cross-linked polymer is manufactured to t around some object, such as the pipes in a petrochemical plant. Electricity is passed through it to heat the pipe. As the material expands, conduction is disrupted. Cross-links cause contraction upon subsequent cooling, reestablishing conduction. 6. Fibermatrix composites Radiation-cross-linking of bermatrix composites using an electron beam is a promising application which has been developed in recent years. The work has involved epoxy resins with varying bers such as carbon or aromatic polyamide. Both radical and cationic cross-linking mechanisms can occur [89]. Cationic curing is achieved through the incorporation of initiators such as diaryliodonium or triarylsulfonium salts [90]. The materials development eorts have aimed at structural applications for aerospace [90] and for boat-building [91]; other applications, including automotive use, are also of interest. There are a number of advantages to e-beam curing of composites, compared with conventional thermal processing [9295]. Curing at ambient
temperature allows tighter control of part dimensions, and elimination of internal stresses which otherwise occur on cooling and which reduce material strength. Curing times are shorter, and the resins (which are not designed to cure thermally) are more stable and thus have longer shelf life. In addition, the e-beam process has environmental advantages because emission of volatiles is much lower. One aerospace rm is reportedly applying the process in production of large components such as rocket motor housings. 7. Chain scissioning (and oxidation) Important commercial applications utilize radiation to improve processing properties and/or materials-compatibility parameters, through processes which may be loosely termed ``degradation,'' and that involve chain scissioning, chain branching, and/or partial oxidation of macromolecular materials. PTFE is an inherently chainscissioning polymer. E-beam irradiation of PTFE in air results in the production of micropowders having lower molecular weight, and having carboxylic acid groups which reduce hydrophobic and oleophobic properties [96100]. The e-beam treatment of PTFE is now a large commercial industry. The treated PTFE shows greatly enhanced compatibility with other materials, and can be incorporated as an additive into inks and coatings. PP has inherently low melt strength. Irradiation of PP under inert atmosphere causes a combination of chain scissioning and long-chain branching, and results in a material with signicantly enhanced melt strength. This process, which is sometimes termed ``vis-breaking,'' thus provides improvement of rheological properties. This allows dierent molding options for PP, and allows easier conversion of PP into bers. This technology has been the subject of a number of patents, and has been incorporated into commercial processing of PP items [101,102]. Irradiation of certain non-polar polymers in the presence of air has been used as a means of creating some concentration of oxidative groups in the material, thereby improving miscibility with polymers having higher polarity, and facilitating
15
the preparation of miscible blends. For example, polyethylenepolyamide blends have been prepared using PE that had undergone radiationoxidation [103,104]. Oxidation carried out specically at the surfaces of powders, lms, etc., for similar compatibilization purposes is discussed in the following section. 8. Surface modication Radiation treatment is being extensively investigated as a means of altering surface properties of polymeric materials, including lms, bers, powders and molded objects. Much of the work has involved the irradiation of non-polar polyolens (PE, PS, PP, uoropolymers, etc.) as a means of inducing polar groups at surfaces, in order to enhance such properties as printability, wetability, adhesion with other materials or with biological components, compatibility (as in the production of material blends using two immiscible polymers), or further chemical modication [105110]. Often such irradiations take place in the presence of (or involve subsequent exposure to) reactive gasses such as O2 or NH3 , in order to form reactive polar groups at the surfaces (carboxylic acids, alcohols, amines, etc.). While ions, electrons, and gamma rays have all been utilized in surface treatment schemes, ions and low-energy electrons are particularly well suited for such applications due to their inherently limited penetration depth. This has two advantages. Surface properties can be altered, while bulk properties are unchanged. Furthermore, the energy utilized in the surface treatment process is not wasted via penetration of the radiation into or through the sample. Numerous papers have appeared in recent years describing surface treatment using ions. Surface modication with ions typically involves uences of $ 109 to $ 1014 ions=cm2 [111] or in some cases, 1015 ions=cm2 ; higher uences may result in destruction of the polymer, generally through carbonization [111]. While most irradiations have used positive ions, it has been reported that the use of a negative ion beam reduces the problem of surface charging [112].
To provide a basis for understanding the relationship between surface alteration and changes in surface properties, a number of studies have identied the chemical changes on polymer surfaces induced by irradiation, including reactions involving reactive gasses or water [113116]. It is also shown that irradiation with ions of certain elements results in permanent incorporation of the element in signicant concentrations into the material surface structure. For instance nitrogen has been incorporated in this way into the surface region of PS and PE in concentrations of $ 10% [113,117]. It has also been observed that alterations in surface morphology that can occur upon irradiation (which correspond to increased surface roughness) contribute to enhanced adhesion properties of irradiated materials [118,119]. Using high-intensity pulsed ion beams, dramatic increases in surface area and roughness can be achieved: the surfaces of PTFE, polycarbonate, polyimide and other materials can be turned into a microcellular foam [120,121]. In the development of new bermatrix composites, surface treatment of ultra-highstrength PE bers with a single high-intensity pulse of Ar ions resulted in dramatic improvement in adhesion within an epoxy matrix, due to a combination of surface roughening through ablation, and enhanced surface polarity due to oxidation [122]. The opposite eect, surface smoothing, has been demonstrated using an e- beam at low voltage to expose foamed sheet materials. The resulting smooth surface layer on the top of the foam provides advantages in printability, adhesion and mechanical properties [123]. Ion beam irradiation of polymer surfaces has been shown by a number of investigators to improve subsequent metalization with elements such as Cu and Al [119,124,125]. Polymermetal adhesion has been reported to improve by as much as a factor of 10 when ion irradiation is employed [124]. Irradiation of PS, PP, or a siloxane with ions can bring about a signicant increase in the adhesion and proliferation of living cells on the polymer surfaces, which has implications for biocompatibility of implants and for laboratory
16
culturing of tissue [112,126129]. Similarly, irradiation of polymer surfaces with either an ion or an electron beam promotes adhesion of antibodies and proteins, which is of interest in the development of ecient immunoassays [128,130]. Irradiation with ions is reported to be useful in producing surfaces of enhanced stability and durability. For example Lee and others have reported dramatic improvements in abrasion resistance, as well as lowered friction coecients, for materials such as polycarbonate and PMMA after exposure to high uxes of ions [131,132]. The wear resistance of ultra high-molecular weight polyethylene, which is used in hip joint replacements, has been reported to show dramatic improvement following ion beam irradiation [133,134]. The temperature at which photoresist layers (used in microlithography) begin to decompose, can be increased by ion beam exposure, [135,136] as can the photostability of traditional Japanese lacquer coatings [137]. Implantation of Al ions into the surface layers of polymers such as polyimide aords protection against aggressive oxidative environments such as low earth orbit, by giving graded surface-region oxide layers upon oxidation; this appears to be superior to brittle thin-layer inorganic coatings [138]. Schemes for producing surface layers on polymers, having high electrical conductivity, have been demonstrated using ion beam treatment [139, 140]. For example, exposure of PE to Ar or Xe ions yields a surface which will bind ions from a LiCl solution, giving a conductive surface layer [139]. 9. Grafting Grafting is a radiation technology which has been widely explored [141,142], yet extensive publications describing development eorts in this area continue to appear, due to the broad applicability of the technique to addressing material property needs [143158]. Grafting is used in situations where the requirements for bulk properties and surface properties cannot be readily met using a single polymeric material. The beauty of grafting is that it is possible to construct a material whose
bulk is comprised of one polymer type but whose surface is made of a dierent polymer type. Grafting allows the selection of virtually any combination of bulk and surface materials. Using this approach, one begins with a bulk material (often chosen on the basis of good mechanical strength and low cost), and then ``grows'' a second polymer type on the material's surface. Radiation provides a highly advantageous means of grafting. A large concentration of free radicals is produced in the irradiated material without the use of chemical initiators. These radicals undergo reaction with a monomer of choice to produce macromolecular chains that are covalently bound to the irradiated specimen. Many geometries, including lms, powders and macroscopic objects, have had surface grafts attached in this way. A wide range of graft layers has been produced by varying available parameters: utilizing dierent monomers or combinations of monomers, adding cross-linking agents, choosing conditions to vary the depth of penetration of monomer into the bulk, etc. By this means, bulk materials are provided with ``tailor made'' surfaces; promising products have been developed in which a grafted layer provides the required compatibility with a particular species which may be ions, aqueous media, metals, or biological substances. Many of the grafting processes that have been reported to date have involved relatively hydrophobic polymers which have been given a hydrophilic surface layer using a monomer such as an acrylate, to facilitate interaction with aqueous or ionic substrates. In the ``direct'' or ``simultaneous'' method of grafting, a polymer is irradiated in the presence of a monomer or monomer-containing solution; often the solution contains an inhibitor to retard homopolymerization in the liquid phase. Alternatively, the polymer can be rst irradiated and then subsequently placed into contact with monomer (the ``preirradiation'' method). In a variation of the latter approach (the ``peroxidation'' method), a material is irradiated in the presence of air. The grafting step can be performed much later; peroxides formed during irradiation can be activated by elevated temperature to form radicals at the desired time.
17
Grafting has been extensively employed for immobilization of enzymes for use in biocatalysis of utility to synthetic organic chemists [159164]. Often, a polymer such as polyacrylic acid is grafted onto a substrate, and the enzyme is then bound to the grafted layer. Binding allows for easy recovery, facilitating purication of the product and in many cases reuse of the enzyme. Enzyme stability is often enhanced in the bound state. Many dierent enzymes have been attached to powders, polymeric microspheres, and other surfaces in this way. Chromatographic supports, for use in purication of proteins by anity chromatography, are also prepared by radiation grafting of polymers having ionic and or polar groups onto powders, hollow bers, and other substrates [165168]. Numerous reports have described the grafting of polymers, such as acrylates, onto bers and fabrics. Most frequently, the grafting treatment renders the ber more hydrophyllic, which is of particular interest for enhanced dyeability. A wide range of bers have been benecially grafted, including PP, nylon and wool [169175]. Grafting of hydrophylic polymers onto highsurface-area substrates to yield materials of high ion-binding capacity has been the subject of many publications [176188]. These materials have been developed for use in removal of heavy metal ions (Pb, Cu, etc.) in the treatment of industrial waste water, and for capture of U ions in the treatment of liquid radioactive waste. Ion-binding materials prepared in this way are also being tested for harvesting uranium from the ocean, and for use as battery membranes. Radiation grafting onto surfaces has been used to enhance biocompatibility or to provide desired biochemical properties [189]. Creating a surface layer of a hydrophylic polymer, in some cases followed by the bonding of a small molecule such as heparin [190], has been reported to be useful in controlling the blood coagulation response toward materials [190193]. Other biocompatibility studies involving grafting [194] have led to enhanced cell adhesion [195] on polymer substrates. Research on grafted materials to meet a variety of other surface property requirements remains active; examples in recent years include membranes for gas separation [196], adhesive layers
[197], enhanced binding of liquid crystal layers [198,199], and surface attachment of organic layers to inorganic llers to enhance compatibility with polymer matrices [200,201]. Methods for making grafting technology more versatile are also under ongoing development. Recent reports continue to explore the use of multifunctional additives and chargetransfer complexes to enhance grafting yield [202204]. The use of supercritical CO2 to enhance monomer penetration into the surface undergoing grafting [205], and the use of heavy-ion beam irradiation to yield surfaces with only partial graft coverage [206208] have been explored. The addition of acids and salts to enhance grafting yield is a widely used technique [141]. 10. Hydrogels Research on the use of radiation in the production of hydrogels has become intense during more than a decade [209]; interest has grown continuously, and a large number of papers have been published over the past few years. Numerous applications have been found or envisioned for these materials, particularly in the biomedical arena [210213]. Uses include: wound dressings, soft contact lenses, controlled-release drug delivery systems, articial skin, water absorbents, and adsorbents for metal ions or enzymes for purication or catalysis applications. Some hydrogel applications have been undergoing commercialization; most notably, hydrogels sold for application as coverings for burns and wounds are coming into wide use in many countries. The hydrogel dressings provide many desirable properties [209,214216]. They maintain a moist environment, and provide a barrier to bacterial contamination while allowing oxygen access to the injured area. They can be removed without damage to the healing surface. An increased healing rate is reported, compared with dry gauze dressing [217]. Hydrogels consist of a three-dimensional network of hydrophyllic polymer chains (polyvinylpyrolidone, polyacrylamide, polyvinylalcohol, etc.) which can be swollen with water. The materials usually contain a much higher amount of water
18
than of polymer [218]. Some gels can reach extremely high proportions of water, and are referred to as ``superabsorbent'' materials [214,219]. ``Permanent'' hydrogels require that the polymer chains be cross-linked by covalent chemical bonds as opposed to reversible interactions such as hydrogen bonds. This cross-linking can be readily achieved using ionizing radiation, which can be employed with a wide range of polymer types, can be done at room temperature, and does not require the addition of initiators or additives that can leave undesired residues. An advantageous means of producing hydrogels for medical application is to start with the polymer and water inside of a sealed package, and then submit this solution to ionizing radiation [218]. The nished product thus makes use of radiation in two ways simultaneously: cross-linking and sterilization. A number of interesting variations on hydrogel materials have been reported in recent years. Hydrogels have been grafted onto surfaces, or into pores of materials, for purposes of achieving hydrophylic characteristics or biocompatibility. Fabrics having hydrophylic materials grafted to their surfaces are being investigated as reinforcing agents for use in enhancing the strength of hydrogels [220]. Radiation cross-linking of naturally occurring polymers such as polysaccharides, is being investigated for production of biodegradable hydrogels [221,222]. ``Nanogel'' materials, consisting of individual macromolecules that are internally cross-linked by irradiation of dilute solutions, have been described [223]. Specially modied hydrogels are being studied for waste water purication. Gels containing acid groups have been made to bind ions, including uranium and nickel, for use in removal of metals from aqueous media [224226]. Other hydrogels have been used to demonstrate the scavenging of textile dye molecules for purication of waste water streams [227]. Enzyme adsorption into hydrogels has been studied for use in industrial processes. For example amylase (used in the fermentation industry) was shown to retain its activity for a longer time when bound to a gel [228]. Bound catalysts have a number of advantages including easy separation after processing.
A fascinating type of hydrogel, that is the subject of extensive investigation, is responsive to environmental factors [229231]. Thermally responsive gels (sometimes referred to as `ìntelligent'' gels) undergo a transition over a relatively narrow temperature range. Below the critical temperature, the polymer has high compatibility with water and exists in a fully swollen gel state. Above the critical temperature, the polymer is more compatible with itself than with the water, and the macromolecules begin to coil up together with the result that water is expelled from the gel [232,233]. For example, poly(N-isopropylacrylamide) gels, prepared by e-beam cross-linking, exhibit a critical temperature of 32 C [234]. Radiation-cross-linked hydrogels are reported to undergo the swelling/deswelling phenomenon more rapidly than conventionally cross-linked gels [234, 235]. Certain hydrogels can be made to undergo a similar type of transition due to other environmental factors, for example being pH-responsive or electro-responsive [236,237]. Hydrogel materials exhibiting the responsive phenomenon have received much attention for application in controlled release of drugs [238 243]. By repeated contraction/expansion cycles, it is possible to release pulses of small molecules dissolved in the hydrogel matrix [244]. An ono device based on an electroresponsive hydrogel that releases a drug molecule is being developed [245]. By attachment to an appropriate sensor, such a system could be made to function automatically in response to a stimulus for instance, it may be possible to release insulin in response to glucose blood levels. In vivo studies have been carried out in which hydrogels operating in a non-pulsed mode were implanted into diabetic rats; the hydrogel provided a steady low-level release of insulin which gave a reduction in their hypoglycemic condition over a period of two months [246]. A variety of other uses for responsive hydrogels are being investigated, including such things as articial muscles, valves and actuators [247]. One interesting material recently reported, a responsive biomembrane, made use of radiation processing in three ways: porosity induced by an ion beam followed by etching, immobilization of an enzyme, and cross-linking of a hydrogel [248].
19
11. Sterilization In developed countries, radiation sterilization of disposable plastic medical items exceeds 50% of all such equipment [1], versus the older technique of chemical treatment with ethylene oxide. The percentage of such radiation-sterilized plastics continues increasing steadily [15,249251]. A major driver for conversion to radiation sterilization is the elimination of toxic chemical residue from the product [252], and also safety and environmental considerations in the sterilization process. A wide range of commercial medical products is now sterilized using either e-beam or gamma irradiation, including vials, tubing, gauze, sponges, syringes and tissue-culture asks. Radiation sterilization of food wrap and pharmaceutical packaging is an emerging application [253]. In this usage, the food or pharmaceutical product would be enclosed in the packaging prior to sterilization, so that the contents and the wrap would be simultaneously irradiated. One issue is the potential generation of radiolysis products which might migrate into the contents. This aspect continues to be the subject of investigation [254256]. Technology development for implementing ionizing radiation as a means of sterilizing disposable plastic medical equipment has been an effort primarily of addressing radiation stability problems for polymeric materials. Degradation problems encountered include post-irradiation oxidation of polymers due to reactive species (such as radicals trapped in crystalline regions) which arise during the radiation exposure. This causes deterioration of mechanical properties which occurs slowly over the course of months or years, due to oxidative chain scission reactions, while the items await use on storage shelves. PP, used widely in the manufacture of syringes, is especially problematic, due to its semicrystalline nature and high susceptability to radiation-oxidative degradation. Color is also an issue for many materials. Most polymers turn yellow or brown upon exposure to relatively low radiation doses, due partly to inherent color center formation of macromolecular materials arising from a combination of trapped radicals and permanent structural changes in the
macromolecules which include conjugated chromaphores [257,258]. The coloration is a complex phenomenon; oxygen diusing through the material reacts with radicals and causes bleaching of the radical-based color centers [259]. The discoloration can also arise due to chemical reactions of commonly used hindered phenol type antioxidants. The degradation problems have been eectively solved for a number of materials and applications for example ``radiation grade'' PP materials are now available [260265]. Choosing antioxidants which give reduced color formation, while maintaining the ability to prevent radiation reactions leading to mechanical property deterioration, is important. Copolymers can be used to decrease crystallinity, promoting recombination of radicals to avoid long-term oxidation eects. For PP, 23% of ethylene monomer may be incorporated. There are also processing parameters that can be changed to aect the morphology and crystallinity of the material, and plasticizers that can enhance radical mobility and promote recombination. Methodologies for more reliable lifetime prediction based on accelerated laboratory tests have been developed [266]. A typical dose for radiation sterilization would be on the order of 2.5 Mrad. The dose at which material properties are signicantly aected varies tremendously among dierent polymer types, and depends on irradiation conditions. Tables that give ranges of relative radiation resistance of all the common polymer types, and which include data for both oxidizing and non-oxidizing conditions, have been made available for use in selecting polymers for applications, such as sterilization, which necessitate exposure to ionizing radiation [267,268]. One important medical application requiring more work is the use of radiation in sterilizing UHMWPE hip and knee joint replacements. This application is now in commercial use; however, long-term degradation appears to be a limitation to the lifetime of these prostheses. Post-irradiation storage under nitrogen has been recommended [269]; research is continuing on this problem [269273]. A relatively new application under evaluation is the use of gamma radiation in the conservation of
20
objects consisting of natural polymers. Irradiation has been particularly explored in the preservation of books [274] but its use with other historic or archaeological objects consisting of leather, cloth, wood, etc. can be envisioned. The radiation kills mold and fungus, and arrests the biodegradation processes. Together with the sterilization, radiation-grafting of monomers for purposes of strengthening and protecting the material (such as paper) can be carried out [275]. One issue needing further examination is assuring the minimization of potential post-treatment, time-dependent degradation caused by the radiation itself. 12. Modication of wood and other natural products Radiation has been applied to a wide variety of low-value natural products in order to upgrade them into products having enhanced properties. Wood, cellulose, starch, cotton, wool, pine needles, straw, peanut shells, and many other agricultural commodities and byproducts have been the subject of experiments. Three basic types of products based on polymers, wood and radiation have been produced: woodplastic composites (WPC), woodber reinforced plastics, and laminated WPCs [276]. Production of WPCs is achieved by impregnation of acrylates, styrene, vinyl acetate, or other crosslinkable monomer into wood, followed by polymerization using gamma or e-beam exposure, to yield materials with greatly enhanced hardness, tensile strength, scratch resistance, moisture repellency and resistance to biodegradation [277 280]. This process takes advantage of the high porosity of wood, which consists of up to 80% voids. Commercial products utilizing WPCs include ooring and table tops. Woodber composites make use of wood bers dispersed within a polymer matrix [281]. Laminated WPCs are wood panels with coatings of cross-linked resin; often, multiple coating layers are used. Partial breakdown of cellulose from wood pulp by chemical treatment, to yield an intermediate called viscose, is a large-scale industrial chemical process used in the manufacture of a variety of products such as rayon bers, lament, cord, lm
and packaging. Due to environmental regulations, the industry is being forced to reduce chemical emissions; some plants have been forced to close. The application of e-beam treatment in the decomposition of cellulose has been shown to be of great utility in the production of viscose by reducing the chemical processing necessary [282 286]. Modication of cotton cellulose is similarly enhanced by gamma exposure [287289]. Very diverse applications of radiation and agricultural products have been investigated; a few examples from recent years are listed here. The use of e-beam processing in development of materials based on starch, including biodegradable composites and foams, is under investigation [290,291]. Radiation grafting of materials onto cellulose and starch has been carried out [292297] to enhance thermal stability, microbial resistance and water absorbance; for example grafting of monomers such as acrylamide onto starch yields superabsorbant materials. Radiation-treatment of chitosan and chitosanpolymer blends is being explored [298]. Partial breakdown of agricultural waste products, such as the shells of cotton and soybean seeds, using gamma exposure and chemical treatment, is shown to boost the nutritive value of these materials when fed to livestock [299]. Calcium caseinate, a protein-based material obtained from milk, can easily be cast into lms. In order to be useful, gamma irradiation of the lms is necessary to induce cross-linking which enhances strength and provides resistance to dissolution in water, rendering the lms potentially applicable as biodegradable, edible materials for food packaging or for microencapsulation of medication [300304]. 13. Plastics recycling Solid waste is an important worldwide problem. Approximately 25 million tons of plastic appeared in the municipal solid waste of the US in 1996 [305], most of which was buried in landll. The percentage of polymer scrap in the waste stream has grown steadily: in 1960, polymers accounted for only 0.5% of solid waste in the US; by 1980 that gure had grown to 5.0%; by 1996, it
21
reached 12.3% [305]. The ve dominant polymer types in the US municipal waste are: LDPE (5 million tons per year), HDPE (4.1 million tons), PP (2.6 million tons), PS (2 million tons), and PET (1.7 million tons) [305]. One technological barrier to polymer recycling is the incompatibility of dierent polymer types. When an attempt is made to mold a product using a polymer mixture, the materials typically form separate phases, resulting in poor properties. Another problem is degradation that may be present in the recycled material: properties are aected by changes in molecular structure caused by environmental factors during use, including UV light, thermal-oxidative processes, attack by pollutant gasses, chemical interaction with liquid contents, and others. Ionizing radiation oers unique possibilities for application to the problem of recycling polymers [306], due to its ability to cause cross-linking or scission of a wide range of materials without dissolving the sample or having some chemical initiator incorporated in the matrix. Possibilities for using radiation in recycling include: (1) enhancing the mechanical properties of recovered materials or blends, principally through cross-linking, or through surface modication of dierent phases being combined; (2) decomposition of polymers, particularly through chain scission, leading to recovery of low molecular weight mixtures (termed ``chemical recycling''). Irradiation of recovered LDPE samples [307,308], blends of LDPE and HDPE mixedwaste [309], and mixed compositions of PET and PE which had been coextruded [310], has been described. Radiation-induced oxidation of PE prior to blending with recycled polyethyleneterephthalate (PET) was particularly benecial; this enhanced the miscibility of the PE with the more polar PET [311]. The addition of cross-linking agents to compositions representing recovered waste materials has been investigated. Mixed materials containing HDPE, PP and PS, with 210% of triallyl cyanurate (TAC) added, showed signicant improvement in modulus at a dose of $2035 Mrad [312]. In other studies, good quality foams could be produced using e-beam irradiated, recycled LDPE,
when multifunctional acrylates were incorporated [313]. Recycled, reinforced polymer systems have been successfully prepared using PP from reprocessed automobile bumpers [314318]. A variety of bers were used, including wood, glass, and waste cord-yarns from the tire industry. Reactive additives (such as epoxy acrylate) were incorporated to enhance bonding between the materials. Signicant improvement in properties upon e-beam irradiation was noted for a number of compositions. The approach is particularly interesting since many of the bers employed are either low-cost materials, and/or materials which themselves have been recycled. Recycling of butyl rubber from inner tubes, using irradiation of cryogenically ground rubber crumb, is a commercial process in China [319], which leaves few rening wastes. The irradiated rubber particulate is mixed with virgin rubber resin to yield moldable composites that are made into inner tubes and into waterproong materials for coating applications. A limited amount of work has been reported on the use of radiation in chemical recycling (degradation) of polymers, yielding liquids of mixed composition for potential use in the petrochemical industry. Irradiation of PP allowed its subsequent catalytic pyrolysis to be carried out at a much lower temperature, and altered the resulting compounds. These results indicate that radiation can be useful in lowering the energy requirements for chemical recycling, as well as providing a means of controlling the nature of the products [320]. Some of the highest-volume polymers going into the solid land ll (HDPE, LDPE, PP) are known to inherently cross-link under irradiation; however, when irradiated in the presence of air, such materials can undergo predominantly oxidative degradation [321], leaving open the possibility of chemical recycling using, for example, low dose rate gamma exposure. Another study reported that when particles of radiation-cross-linked polyethylene were incorporated as an additive into a melt of uncross-linked polyethylene, an enhancement of elasticity was obtained [322,323]. This observation may not only provide an attractive solution to the problem of
22
recycling a cross-linked material, but it may indicate the possibility of cross-linking ordinary waste polyethylene by radiation in order to prepare a value-added ller. 14. Ceramic precursors One specialty application of radiation processing is the production of silicon carbide ber from a precursor polymer [324,325]. A polymer containing silicon and carbon (polycarbosilane) is crosslinked by irradiation to a high dose, after which the material is heated to a temperature of about 1200 C to form silicon carbide. Fibers of silicon carbide are used to make ceramic and metal composites for high-performance, high-temperature applications. The material prepared by this process has signicantly better stability than silicon carbide ber made by conventional means of pyrolysis without preirradiation. This technology has been commercialized. More recently, this approach has been extended to the production of silicon nitride bers [326]. The radiation-cross-linked polycarbosilane is pyrolyzed at 1000 C in the presence of NH3 gas to yield Si3 N4 , which has been processed into cloth and used in making an electrical wire insulator which has high thermal stability (up to 1300 C). This material is being explored for use in aggressive environments such as nuclear power plants, steel-production plants and aerospace applications. 15. Electronic property materials High-energy irradiation of polymers can convert them from dielectric materials to materials having electrical conductivity, and this creates opportunities for use of radiation in producing specialty materials for electronic applications. Electrical conductivity of organic materials can be greatly increased during the time that the specimen is exposed to a radiation ux, due to the creation of transient conductive species (electrons, holes) which rapidly recombine once the irradiation is stopped, with the result that the conductivity
quickly decreases to near the initial value [327]. Following relatively high absorbed dose, however, permanent changes in conductivity occur; and it is primarily this latter eect which is being examined for possible application to production of polymerbased electronic materials. The mechanism of permanent induced conductivity has been the subject of some debate, but the formation of a carbonaceous network within the material appears to be a dominant eect [328 332]. Irradiation with various ions (including Ar ; Ni3 ), to total uences of 1015 1017 ions=cm2 induces dramatic conductivity changes in materials such as polyimide and polyethylene [329331,333]; conductivity enhancements on the order of 1013 have been reported [329]. Irradiation of conjugated polymers, such as polypyrole or polyaniline, is being investigated as an alternative to chemical doping, as a means to render them electrically conductive [334,335]. For example, as an alternative to relatively harsh treatment with an external acid source to convert polyaniline to its conductive form, it was shown that PVC could be incorporated into the material, from which HCl could be liberated upon irradiation [336]. Use of ion irradiation in production of structures such as sandwich layers of dielectric/conductive/dielectric materials intended for fabrication of transistorlike switches [337], or of nanoscale devices from irradiation of self-assembled monolayers [338], is being pursued. Following electron irradiation to high dose, certain ferroelectric copolymers exhibit the phenomenon of electrostriction: under the inuence of an electric eld the specimen undergoes a contraction in size [339,340]. This phenomenon is presently not well understood. The electrostriction is reversible, and can operate to high frequencies (>100 kHz). These materials are being further examined for potential use in construction of transducers and other devices. 16. Ion track membranes Currently, one of the most exciting developments in radiation processing of polymers is the creation of microporous and nanoporous mem-
23
branes having highly uniform geometry. These remarkable materials can be made by irradiation of thin polymer lms with swift heavy ions, such Au ; Xe or U , often using energies on the order of 10 MeV, to create latent radiation-damage tracks through the sample. Following etching with a solution of NaOH, uniform cylindrical pores through the material can be obtained [341344]. Many dierent polymers can be utilized; PET, and polycarbonate have been used in a number of studies. Track-to-bulk etching rates of > 500 are found; improvement of the etching process has been achieved by exposure of the irradiated materials to UV, ozone, thermal or chemical treatments. Pore sizes in ion track membranes can be controlled by etching conditions and by choice of irradiation treatment. Cylindrical channels 0.025.0 lm in diameter are readily obtained with lengths of 1050 lm [345,346]. Very small pore sizes are also possible: for example, 10100 nm pores have been reported [347351]. Eorts to generate pores of high-aspect ratio have been successful, yielding values up to $ 103 [352]. Membranes containing anywhere from a single pore up to 109 pores=cm2 have been produced [353]. Thin-lm polymer membranes having highly uniform pore size have been made available commercially (Nuclepore is a provider); these have been primarily used for laboratory ltration applications. Particularly interesting are experiments by a number of dierent research groups, in which selected substances are being chemically bound to the pore walls, to yield semipermeable membranes having highly selective properties. Specially tailored microporous materials produced by non-radiation processes are in extensive industrial use for separation or purication of liquids and gases. A large number of industrial processes are dependent upon such ltration schemes, including: purication of drinking water; desalination; separation of N2 and other species from air; food and beverage processing; separations in the petrochemical industry; and purication of biological and medicinal materials. The new class of membranes of highly regular geometry and chemical properties, created by ion tracks, has great potential to undergo design/modication
for impacting these many applications [354], and a urry of activity is now getting underway in adapting these materials to commercial use. For example, work is proceeding in fabrication of humidity sensors based on ion track membranes made from Kapton, taking advantage of their large internal surface area for binding water; electrical property measurement is utilized to monitor the moisture content [355]. Other workers are applying thin polymer coatings on ion track membranes to alter properties such as hydrophobicity, bactericidal tendencies, etc. [356]. A number of researchers have succeeded in grafting stimulus-responsive polymers (hydrogels) into the pores of ion track membranes. For instance, a membrane composed of PET with pore size of $1 lm and pore density $ 106 =cm2 , was grafted with n-isopropylacrylamide from a solution, under gamma exposure [357]. Swelling and contraction of the gel material could be thermally controlled over a narrow temperature range; the transition temperature (33 C) of the graft is similar to that of the bulk poly-n-isopropylacrylamide. The porosity of these grafted membranes can thus be modulated by an external stimulus such as temperature (also pH or electric eld), so that the pores can be cycled open and closed repeatedly over long time periods by varying the environmental factor back and forth [353,358 360]. Permeability measurements have shown that the transmittance of a variety of dierent molecules (including dyes, proteins or water), through these membranes can thus be turned on and o at will. Potential applications include the controlled release of drugs. These so-called `ìntelligent'' membranes are mechanically stable. One additional application of interest for iontrack membranes involves the electrodeposition of metallic nanowires, and also hollow nanotubes of various compositions, into the pores [352,361 363]. These structures show electronic and other properties dierent from the bulk materials. 17. Micro-device production (lithography) Another exciting application of polymer radiation processing that is now emerging is in the
24
production of microelectronic circuits, micromachines, and other ultra-small devices [364]. Radiation-based technology using X-rays, e-beams, and ion beams is the key step in a variety of different approaches to micropatterning. The polymers used for patterning technologies range from simple materials such as PMMA, to complex macromolecules designed especially for the application, which may be used in conjunction with a low molecular weight compound (such as an `àcid generator'') [365367]. Such additives produce an active intermediate in the presence of radiation which then catalyzes a transformation of many sites on polymer molecules, in a chain reaction process, thus providing the material with high sensitivity to radiation (high-G yield). Lithography functions through radiation-induced chemistry which brings about a change in solubility of polymer molecules in the exposed regions. This can be due either to chain scission, cross-linking, or else side-group modication that results in an alteration of the polarity of the material. Both ``negative'' and ``positive'' resist types are used: a negative resist becomes less soluble upon exposure; a positive resist becomes more soluble upon exposure. In either case, a subsequent solvent development step removes the more soluble material, leaving a patterned polymer surface. 17.1. X-ray and e-beam lithography for microelectronic circuits One application with tremendous commercial potential is radiation technology for microlithography. In the past decades, computer power has increased steadily as feature sizes of microelectronic circuits have been made continually smaller [368,369]; progressively more circuitry is being put onto chips. The conventional lithography process used for making computer chips involves patterning, with light, of a thin polymer layer that is spin-coated on a silicon wafer, but this photolithography is reaching a limitation due to diraction eects: the processing wavelengths that are being used now are about the same size as the feature sizes in the microcircuits. In order to continue shrinking features on computer chips and making computers ever more
powerful and economical, it will now be necessary to go to radiation-based microlithography. There are two main competing technologies under development right now. One is based on an e-beam and is led by Bell Labs together with Texas Instruments, Motorola and Samsung [370,371]. This approach makes use of a 100 keV electron beam with a magnetic lens; patterning is achieved using an electron-scattering mask. A rather similar ebeam lithography eort is underway by IBM and Nikon, with some dierences in the mask design. The second technology is based on soft X-rays (13.4 nm) generated from an Nd:YAG laserinduced plasma source, with a mask and optics allowing a 10 image reduction [372,373]. This eort combines three National labs (Sandia, Lawrence Berkeley, and Lawrence Livermore), and three corporations (Intel, Motorola, AMD). Both the e-beam and the soft X-ray technologies are capable of patterning all the way down to lines and spaces under 70 nm considerably smaller than the current commercial applications, which have lines and spaces down to about 180 nm. It is likely that by the beginning of the next decade, all computers being sold will be powered with chips made by radiation patterned microlithography. This may provide the largest economic impact of any radiation processing technology so far. Ion beams are also being investigated for patterning of microcircuits, including a novel approach in which patterns are written onto conductive polymer layers, onto which copper can then be deposited to yield a structured metal layer [374]. 17.2. LIGA The LIGA process (LIthographie, Galvanoformung, Abformung) uses X-ray radiation from a synchrotron to carry out ``deep lithography,'' creating patterns in a radiation-sensitive material such as PMMA, for the purpose of producing a variety of ultra-small devices [375]. Unlike lithographic production of microcircuits, where a spincoated layer of polymeric resist material having a thickness on the order of a few microns is sucient for patterning, LIGA involves the patterning of polymer layers several hundred lm thick. This
25
requires the parallelism of synchrotron radiation. Radiation wavelengths between 0.2 and 0.3 nm appear to provide the best compromise between diraction eects (which become worse at longer wavelengths), and electron scattering eects (which become worse at shorter wavelengths). Synchrotron irradiation through metal masks onto PMMA layers, followed by removal through solvent dissolution of the exposed (chain-scissioned) areas, has generated structures, such as honeycombs, of height > 300 lm, with individual wall thickness of $ 4 lm, and with deviations in wall thickness of $ 0:1 lm. The PMMA structures are used as templates in a subsequent step of galvanic deposition of metals. The metal structures are used to produce more polymer-based molds, which can be employed in mass production of more of the small metal parts. This technology was initially developed for production of extremely small nozzle systems needed for uranium enrichment processes, but LIGA has now been applied to a wide range of remarkable ultra-small, complex devices, many having moving parts. Functional LIGA devices now include microscopic motors, sensors, and actuators [376378]. The production of 3-D structures, such as functional ``millimachines'' using LIGA techniques, involves the 90 rotation and assembly of some components. LIGA technology oers the possibility of providing a whole range of revolutionary new miniature mechanical devices allowing dramatic reductions in size, weight, and electrical power. Uses for such microscopic machines are envisioned for everything from aerospace to automobiles, or for such futuristic applications (seeming like science ction today) as miniature robots that could travel through the human bloodstream to take photos or carry out repairs inside the body. 17.3. Deep ion beam lithography (DIBL) Another recently reported technique for producing complex microdevices is also based on radiation patterning. Using a 1-lm-diameter beam of 2 MeV protons, it is possible to directly write deeply penetrating patterns into PMMA or other materials [379,380]. No mask is necessary in this technique; the device reproduces a digitally stored
image by rastering across the substrate. Following solvent development to remove the irradiated regions of the PMMA, complex high-aspect-ratio structures having smooth, submicron walls extending to a height of $ 100 lm from the surface, can be obtained [381]. Assemblies having 3-D features have been produced. This technique is relatively inexpensive compared with synchrotron irradiation. 17.4. Passive optical devices Optical devices for telecommunications are the target of studies into alteration of polymers to create patterned, planar waveguides on substrates. Ultimately, one can also envision the patterning of ``microcircuits'' for computers, for which photons rather than electrons are moved about on a chip, allowing higher speeds and lower power requirements. Ion beam modication of polymers is being pursued to alter index of refraction and also nonlinear optical properties, in research aimed at patterning of optical and optoelectronic devices [382384].
Acknowledgements Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94-AL85000.
References
[1] [2] [3] [4] [5] [6] S. Machi, Radiat. Phys. Chem. 52 (1998) 591. S. Machi, Radiat. Phys. Chem. 47 (1996) 333. S. Machi, Radiat. Phys. Chem. 46 (1995) 399. A.J. Berejka, Radiat. Phys. Chem. 46 (1995) 429. A. Le Moel, R. Spohr, Radiat. Phys. Chem. 46 (1995) 153. R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, American Chemical Society books, Washington, DC, 1996. [7] W. Knolle, C. Trautman (Eds.), Ionizing Radiation and Polymers, Nucl. Instr. and Meth. B 151 (1999). [8] A. Singh, J. Silverman (Eds.), Radiation Processing of Polymers, Hanser, Munich, 1992.
26
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [35] M.E. Haque, N.C. Dafader, F. Akhter, M.U. Ahmad, Radiat. Phys. Chem. 48 (1996) 505. [36] D. Lpez, G. Burillo, in: R.L. Clough, S.W. Shalaby o (Eds.), Radiation Eects on Polymers, American Chemical Society books, Washington, DC, 1991, p. 262. [37] R.A. Jones, W. Punyodom, I.M. Ward, A.F. Johnson, Nucl. Instr. and Meth. B 185 (2001) 163. [38] K. Ueno, Radiat. Phys. Chem. 35 (1990) 126. [39] B.J. Lyons, Radiat. Phys. Chem. 45 (1995) 159. [40] A. Singh, Radiat. Phys. Chem. 60 (2001) 453. [41] A. Singh, K. Bahari, in: L.A. Utracki (Ed.), Polymer Blends Handbook, Kluwer Academic Publishers, Dordrecht, 2001, in press. [42] H. Zhang, J. Xu, Radiat. Phys. Chem. 42 (1993) 117. [43] L. Spenadel, Radiat. Phys. Chem. 14 (1979) 683. [44] J.G.M. van Gisbergen, H.E.H. Meijer, P.J. Lemstra, Polymer 30 (1989) 2153. [45] J.G.M. van Gisbergen, C.P.J.H. Borgmans, M.C.M. Van der Sanden, P.J. Lemstra, Polym. Commun. 31 (1990) 162. [46] J.G.M. van Gisbergen, H.E.H. Meyer, J. Reol. 35 (1991) 63. [47] J. van Gisbergen, N. Overbergh, in: A. Singh, J. Silverman (Eds.), Radiation Processing of Polymers, Oxford University Press, New York, 1992, p. 51. [48] D.J. Gehring, A. Zyball, Radiat. Phys. Chem. 46 (1995) 931. [49] R. Clough, Encyclopedia Polym. Sci. Eng. 13 (1988) 667. [50] J. Sun, Y. Zhang, X. Zhong, X. Zhu, Radiat. Phys. Chem. 44 (1994) 655. [51] A. Oshima, Y. Tabata, H. Kudoh, T. Seguchi, Radiat. Phys. Chem. 45 (1995) 269. [52] T. Seguchi, Radiat. Phys. Chem. 57 (2000) 367. [53] E. Katoh, H. Sugisawa, A. Oshima, Y. Tabata, T. Seguchi, T. Yamazaki, Radiat. Phys. Chem. 54 (1999) 165. [54] U. Lappan, U. Geissler, K. Lunkwitz, Radiat. Phys. Chem. 59 (2000) 317. [55] Y. Tabata, A. Oshima, K. Takashika, T. Seguchi, Radiat. Phys. Chem. 48 (1996) 563. [56] U. Lappan, B. Fuchs, U. Geiler, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [57] Y. Tabata, S. Ikeda, A. Oshima, Nucl. Instr. and Meth. B 185 (2001) 169. [58] R.L. Clough, K.T. Gillen, in: Oxidation Inhibition in Organic Materials, Vol. II, CRC Press, Boca Raton, 1990, p. 191. [59] D.C. McHerron, G.L. Wilkes, in: R.L. Clough, S.W. Shalaby (Eds.), Radiation Eects on Polymers, ACS Symposium Series, Vol. 475, ACS Books, Washington, DC, 1991, p. 220. [60] X. Xiangling, G. Xuewu, Y. Quiang, Z. Zhicheng, Z. Ju, N. Aizhen, Z. Manwei, Radiat. Phys. Chem. 54 (1999) 279. [61] W. Minghong, Z. Ruimin, M. Zue-The, B. Borong, L. Jianqiu, Radiat. Phys. Chem. 49 (1997) 371. [62] A. Safranj, S. Kano, M. Yoshida, H. Omichi, R. Katakai, M. Suzuki, Radiat. Phys. Chem. 46 (1995) 203.
[9] R.L. Clough, S.W. Shalaby (Eds.), Radiation Eects on Polymers, American Chemical Society books, Washington, DC, 1991. [10] V.S. Ivanov, Radiation Chemistry of Polymers, VSP Publishers, Utrecht, 1992. [11] R.J. Woods, A.K. Pikaev, Applied Radiation Chemistry: Radiation Processing, Wiley, New York, 1994. [12] N. Betz, C. Trautmann, A. LeMoel, J.J. Pireaux (Eds.), Proceedings of the Second International Symposium on Ionizing Radiation and Polymers, Nucl. Instr. and Meth. B 131 (1997). [13] A. Charlesby, in: D.W. Clegg, A.A. Collyer (Eds.), Irradiation Eects on Polymers, Elsevier, New York, 1991, p. 39. [14] S. Gallier, Nuclear News (April) (2000) 32. [15] N.A. Halls, in: D.W. Clegg, A.A. Collyer (Eds.), Irradiation Eects on Polymers, Elsevier, New York, 1991, p. 253. [16] A. Berejka, Radiat. Phys. Chem. 42 (1993) 147. [17] V.J. Boaler, in: D.W. Clegg, A.A. Collyer (Eds.), Irradiation Eects on Polymers, Elsevier, New York, 1991, p. 297. [18] A. Berejka, Radiat. Phys. Chem. 46 (1995) 429. [19] A. Chapiro, Radiat. Phys. Chem. 51 (1998) 9. [20] A. Charlesby (Ed.), Atomic Radiation and Polymers, Pergamon, New York, 1960. [21] A.A. Basfar, Radiat. Phys. Chem. 50 (1997) 607. [22] V. Herden, S. Klaum nzer, W. Schnabel, Nucl. Instr. and u Meth. B 146 (1998) 491. [23] V. Dakin, Radiat. Phys. Chem. 45 (1995) 715. [24] A.A. Basfar, M.M. Abdel-Aziz, S. Mofti, Radiat. Phys. Chem. 57 (2000) 405. [25] J. Gehring, Radiat. Phys. Chem. 57 (2000) 361. [26] I. Banik, A.K. Bhowmick, Radiat. Phys. Chem. 58 (2000) 293. [27] D. Cangialosi, P.T. McGrail, G. Emmerson, A. Valenza, E. Calderaro, G. Spadaro, Nucl. Instr. and Meth. B 185 (2001) 262. [28] A.M. Visco, G. Spadaro, F. Scr, E. Calderaro, A. o Valenza, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [29] I. Rangwalla, S.V. Nablo, Radiat. Phys. Chem. 42 (1993) 41. [30] B.J. Lambert, A.A. Basfar, W.J. Chappas, J. Silverman, in: R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, American Chemical Society books, Washington, DC, 1996, p. 206. [31] E.C.L. Cardoso, A.B. Lug~o, L.G. Andrade, E. Silva, a Radiat. Phys. Chem. 52 (1998) 197. [32] S. Tokuda, T. Kemmotsu, Radiat. Phys. Chem. 46 (1995) 905. [33] Z. Ghazali, A.F. Johnson, K.Z. Dahlan, Radiat. Phys. Chem. 55 (1999) 73. [34] V.K. Sharma, J. Mahajan, P.K. Bhattacharyya, Radiat. Phys. Chem. 45 (1995) 695.
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [63] M. Yoshida, M. Asano, J. Kactsu, Y. Morita, Radiat. Phys. Chem. 30 (1987) 39. [64] A. Rembaum, R.C.K. Yen, D.H. Kempner, J. Ugelstad, J. Immun. Meth. 52 (1982) 341. a a [65] A. Sfrny, M. Grasselli, E. Smolko, P. Hargittai, Nucl. Instr. and Meth. B 185 (2001) 254. [66] V.P. Thalacker, Radiat. Phys. Chem. 35 (1990) 18. [67] J.L. Garnett, Radiat. Phys. Chem. 46 (1995) 925. [68] Radtech 2000 UV/EB Conference Proceedings, Published by Radtech International North America, Bethesda, MD, April 2000. [69] K. Lawson, in: RadTech 1998 Proceedings, 1998, p. 1. [70] T.J. Menezes, Radiat. Phys. Chem. 35 (1990) 52. [71] P. Holl, Radiat. Phys. Chem. 46 (1995) 953. [72] V.P. Laricheva, A.F. Korotkiy, V.V. Krayushkin, V.P. Pleshanov, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [73] J.K. Braddock, in: RadTech 2000 Proceedings, 2000, p. 841. [74] J.S. Ross, L.W. Leininger, G.A. Sigel, D. Tian, in: RadTech 2000 Proceedings, 2000, p. 241. [75] W.D. Davies, A. Hancock, I. Hutchinson, B. Williams, in: RadTech 2000 Proceedings, 2000, p. 522. [76] E. Bemporad, F. Carassiti, A. Tata, G. Gallinaro, M. Paris, Radiat. Phys. Chem. 57 (2000) 393. [77] T. Scherzer, Nucl. Instr. and Meth. B 131 (1997) 382. [78] S.V. Nablo, Radiat. Phys. Chem. 35 (1990) 46. [79] T. Ohta, A. Dobashi, T. Ohshima, Radiat. Phys. Chem. 35 (1990) 81. [80] C. Patacz, B. Defoort, X. Coqueret, Radiat. Phys. Chem. 59 (2000) 329. [81] U.V. Lauppi, Radiat. Phys. Chem. 35 (1990) 30. [82] B. Xiao, Y. Zhou, S. Li, M. Luo, X. Wang, P. Zhao, Radiat. Phys. Chem. 57 (2000) 421. [83] S.R. Kerr III, in: RadTech 1998 Proceedings, 1998, p. 610. [84] P. Cook, R. Halperin, Radiat Phys. Chem. 51 (1998) 7. [85] P. Cook, Radiat. Phys. Chem. 35 (1990) 7. [86] S.K. Datta, T.K. Chaki, V.K. Tikku, N.K. Pradhan, A.K. Bhowmick, Radiat. Phys. Chem. 50 (1997) 399. [87] W. Wenyuan, L. Bingzhi, Radiat. Phys. Chem. 46 (1995) 1015. [88] I. Legocka, Z. Zimek, K. Mirkowski, A. Nowicki, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [89] M. Al-Sheikhly, W.L. McLaughlin, Radiat. Phys. Chem. 48 (1996) 201. [90] V.J. Lopata, C.B. Saunders, A. Singh, C.J. Janke, G.E. Wrenn, S.J. Havens, Radiat. Phys. Chem. 56 (1999) 405. [91] W.J. Chappas, B.G. Devney, R.P. Olding, W.L. McLaughlin, Radiat. Phys. Chem. 56 (1999) 417. [92] A. Singh, C.B. Saunders, J.W. Barnard, V.J. Lopata, W. Kremers, T.E. McDougall, M. Chung, M. Tateishi, Radiat. Phys. Chem. 48 (1996) 153. [93] C.B. Saunders, A. Singh, V.J. Lopata, S. Seier, G.D. Boyer, W. Kremers, V.A. Mason, in: R.L. Clough, S.W. Shalaby (Eds.), Radiation Eects on Polymers, ACS
27
[94] [95] [96] [97] [98] [99] [100] [101] [102] [103] [104] [105] [106] [107] [108] [109] [110] [111] [112] [113] [114] [115] [116] [117] [118] [119] [120] [121]
Symposium Series, Vol. 475, ACS Books, Washington, DC, 1991, p. 251. A. Singh, Nucl. Instr. and Meth. B 185 (2001) 50. C. Saunders, V. Lopata, J. Barnard, T. Stepanik, Radiat. Phys. Chem. 57 (2000) 441. K. Lunkwitz, U. Lappan, D. Lehmann, Radiat. Phys. Chem. 57 (2000) 373. A. Ferse, D. Handte, K. Lunkwitz, Plast. Kaustchuk 29 (1982) 458. A.E. Feiring, J.F. Imbalzano, D.L. Kerbow, Trends Polym. Sci. 2 (1994) 26. U. Lappan, U. Geissler, K. Lunkwitz, Nucl. Instr. and Meth. B 151 (1999) 222. K. Schierholz, U. Lappan, K. Lunkwitz, Nucl. Instr. and Meth. B 151 (1999) 232. A.B. Lug~o, B. Hutzler, T. Ojeda, S. Tokumoto, R. a Siemens, K. Makuuchi, A.L. Villavicencio, Radiat. Phys. Chem. 57 (2000) 389. A.J. Berejka, Radiat. Phys. Chem. 46 (1995) 429. A. Valenza, L. Gallo, G. Spadaro, E. Calderaro, D. Acierno, Polym. Eng. Sci. 33 (1993) 1336. H. Raval, S. Devi, Y. Singh, M. Mehta, Polymer 32 (1991) 493. S.K. Koh, S. Park, S. Kim, W. Choi, H. Jung, K. Pae, J. Appl. Polym. Sci. 64 (1997) 1913. W. Choi, S. Koh, H. Jung, J. Vac. Sci. Technol. A 14 (1996) 2366. S. Park, S. Koh, K. Pae, Polym. Eng. Sci. 38 (1998) 1185. S.C. Choi, S. Han, W.K. Choi, H.-J. Jung, S.K. Koh, Nucl. Instr. and Meth. B 152 (1999) 291. G.A. Mesyats, Yu.S. Klyachkin, N.V. Gavrilov, V.N. Mizgulin, R.M. Yakushev, A.V. Kondyurin, Vacuum 47 (1996) 1085. Y. Zhang, A.C.H. Huan, K.L. Tan, E.T. Kang, Nucl. Instr. and Meth. B 168 (2000) 29. D.M. Rck, Nucl. Instr. and Meth. B 166167 (2000) 602. u H. Tsuji, H. Satoh, S. Ikeda, S. Ikemura, Y. Gotoh, J. Ishikawa, Nucl. Instr. and Meth. B 148 (1999) 1136. L. Khler, S. Scaglione, D. Flori, J. Riga, R. Caudano, o Nucl. Instr. and Meth. B 185 (2001) 267. J.C. Caro, U. Lappan, K. Lunkwitz, Nucl. Instr. and Meth. B 151 (1999) 181. C. Pirlot, Z. Mekhalif, J.B. Nagy, J. Delhalle, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. G. Spadaro, D. Acierno, C. Dispenza, E. Calderaro, A. Valenza, Radiat. Phys. Chem. 48 (1996) 207. A. Tth, T. Bell, I. Bert ti, M. Mohai, B. Zelei, Nucl. o o Instr. and Meth. B 148 (1999) 1131. O. G ven, A. Alacakir, E. Tan, Radiat. Phys. Chem. 50 u (1997) 165. H. Kupfer, G.K. Wolf, Nucl. Instr. and Meth. B 166167 (2000) 722. M. Celina, H. Kudoh, T.J. Renk, K.T. Gillen, R.L. Clough, Radiat. Phys. Chem. 51 (1998) 191. M. Celina, H. Kudoh, T.J. Renk, K.T. Gillen, R.L. Clough, Polym. Adv. Technol. 9 (1998) 38.
28
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [148] E. Bucio, R. Aliev, G. Burillo, Radiat. Phys. Chem. 52 (1998) 193. [149] F. Yue-E, J. Jun, M. Chaoxiong, Radiat. Phys. Chem. 54 (1999) 159. [150] S.K. Dutta, A.K. Bhowmick, T.K. Chaki, Radiat. Phys. Chem. 47 (1996) 913. [151] R. Aliev, P. Garc G. Burillo, Radiat. Phys. Chem. 58 a, (2000) 299. [152] E. Bucio, G. Burillo, Radiat. Phys. Chem. 48 (1996) 805. [153] J.L. Garnett, L. Ng, V. Viengkhou, Radiat. Phys. Chem. 56 (1999) 387. [154] I. Kaetsu, Radiat. Phys. Chem. 47 (1996) 419. [155] R. Aliev, R. Navarro Gonzlez, G. Cedillo, Presented at a the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [156] M. Wu, C. Jie, Z. Ding, Z. Me, Radiat. Phys. Chem. 48 (1996) 525. [157] E.A. Hegazy, H.A. Abd El-Rehim, N.A. Khalifa, A. ElHag Ali, Radiat. Phys. Chem. 55 (1999) 219. [158] I. Kaetsu, K. Uchida, H. Shindo, S. Gomi, K. Sutani, Radiat. Phys. Chem. 55 (1999) 193. [159] A.S. Homan, Radiat. Phys. Chem. 18 (1981) 323. [160] I. Kaetsu, Radiat. Phys. Chem. 25 (1985) 517. [161] N.A. Dung, N.D. Huyen, N.D. Hang, T.T. Canh, Radiat. Phys. Chem. 46 (1995) 1037. [162] A.A. De Queiroz, R.R. Vargas, O.Z. Higa, E.R. Barrak, E.J.H. Bechara, B. Wlasdislaw, L. Marzorati, Radiat. Phys. Chem. 55 (1999) 345. [163] L.M. Ferreira, J.M.S. Rocha, M.E. Andrade, M.H. Gil, Radiat. Phys. Chem. 52 (1998) 207. [164] A.M. Gonchar, V.L. Auslender, Radiat. Phys. Chem. 52 (1998) 213. [165] S. Tsuneda, K. Saito, T. Sugo, K. Makuuchi, Radiat. Phys. Chem. 46 (1995) 239. [166] M. Grasselli, A.A.N. del Ca~ izo, S.A. Camperi, F.J. n Wolman, E.E. Smolko, O. Cascone, Radiat. Phys. Chem. 55 (1999) 203. [167] K. Saito, S. Tsuneda, M. Kim, N. Kubota, K. Sugita, T. Sugo, Radiat. Phys. Chem. 54 (1999) 517. [168] L. Jun, Y. Min, H. Hongfei, Radiat. Phys. Chem. 46 (1995) 847. [169] A.M. El-Naggar, K. El-Salmawi, S.M. Ibraheim, A.H. Zahran, Radiat. Phys. Chem. 49 (1997) 287. [170] A.A. Abdel-Fattah, F.I.A. Said, S. Ebraheem, M. ElKelany, A.A. El Miligy, Radiat. Phys. Chem. 54 (1999) 271. [171] A.M. El Naggar, M.M. Marie, E.H. El Gendy, A.A. El Miligy, Radiat. Phys. Chem. 47 (1996) 623. [172] A.S. Mubarak, A. Khan, K.M. Ali, Radiat. Phys. Chem. 45 (1995) 753. [173] J. Chen, Y.C. Nho, J.S. Park, Radiat. Phys. Chem. 52 (1998) 201. [174] Y.C. Nho, J. Chen, J.H. Jin, Radiat. Phys. Chem. 54 (1999) 317. [175] L. Jianqin, Z. Maolin, H. Hongfei, Radiat. Phys. Chem. 55 (1999) 55.
[122] A.N. Netravali, J.M. Caceres, M.O. Thompson, T.J. Renk, J. Adhesion Sci. Technol. 13 (1999) 1331. [123] T. Kemmotsu, M. Okada, T. Ono, Radiat. Phys. Chem. 42 (1993) 97. [124] D.M. R ck, Nucl. Instr. and Meth. B 166167 (2000) 602. u [125] P. Bertrand, P. Lambert, Y. Travaly, Nucl. Instr. and Meth. B 131 (1997) 71. [126] C. Satriano, G. Marletta, E. Conte, Nucl. Instr. and Meth. B 148 (1999) 1079. [127] M. Kusakabe, Y. Suzuki, M. Kaibara, M. Iwaki, H. Sasabe, Radiat. Phys. Chem. 46 (1995) 263. [128] G. Marletta, C. Satriano, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [129] E. Smolko, R. Mazzei, D. Tadey, D. Lombardo, Nucl. Instr. and Meth. B 185 (2001) 204. [130] A. Safrany, A. Deelder, Radiat. Phys. Chem. 55 (1999) 681. [131] E.H. Lee, G.R. Rao, L.K. Mansur, J. Mater. Res. 7 (1992) 1900. [132] R. Ochsner, A. Kluge, S. Zechel-Malonn, L. Gong, H. Ryssel, Nucl. Instr. and Meth. B 8081 (1993) 1050. [133] J. Chen, F. Zhu, H. Pan, J. Cao, D. Zhu, H. Xu, Q. Cai, J. Shen, L. Chen, Z. He, Nucl. Instr. and Meth. B 169 (2000) 26. [134] C. Allen, A. Bloyce, T. Bell, Tribol. Internat. 29 (1996) 527. [135] U.S. Sias, G. Snchez, J.R. Kaschny, L. Amaral, a M. Behar, D. Fink, Nucl. Instr. and Meth. B 141 (1998) 187. [136] I.T.S. Garcia, F.C. Zawislak, D. Samios, Nucl. Instr. and Meth. B 148 (1999) 1111. [137] K. Awazu, H. Yasui, M. Kasamori, T. Ichikawa, Y. Funada, M. Iwaki, Nucl. Instr. and Meth. B 148 (1999) 1121. [138] Z.A. Iskanderova, J.I. Kleiman, Y. Gudimenko, A. Tkachenko, R.C. Tennyson, I.G. Brown, O.R. Monteiro, Nucl. Instr. and Meth. B 148 (1999) 1090. ck, [139] V. Svor V. Rybka, J. Vac V. Hnatowicz, R. Ochsner, k,
H. Ryssel, Nucl. Instr. and Meth. B 149 (1999) 331. ck, [140] V. Svor K. Prokov, V. Hnatowicz, V. Rybka, Nucl. s a Instr. and Meth. B 149 (1999) 312. [141] P. Dworjanyn, J.L. Garnett, in: A. Singh, J. Silverman (Eds.), Radiation Processing of Polymers, Carl Hanser Verlag, Munich, 1992, p. 93. [142] V.T. Stannett, Radiat. Phys. Chem. 35 (1990) 82. [143] J. Harada, R.T. Chern, V.T. Stannett, in: R.L. Clough, S.W. Shalaby (Eds.), Radiation Eects on Polymers, ACS Symposium Series, Vol. 475, ACS Books, Washington, DC, 1991, p. 238. [144] I. Guilmeau, S. Esnouf, N. Betz, A. Le Mol, Nucl. Instr. e and Meth. B 131 (1997) 270. [145] E.-S. Hegazy, H.A. AbdEl-Rehim, H. Kamal, K.A. Kandeel, Nucl. Instr. and Meth. B 185 (2001) 235. [146] P.S. Majumder, M. Anil, K. Bhowmick, Radiat. Phys. Chem. 53 (1998) 63. [147] K. Friese, F. Tannert, Radiat. Phys. Chem. 55 (1999) 47.
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [176] E-S.A. Hegazy, H. Kamal, N. Maziad, A.M. Dessouki, Nucl. Instr. and Meth. B 151 (1999) 386. [177] B.J. Ringrose, E. Kroni, Radiat. Phys. Chem. 55 (1999) 451. [178] T. Siyam, H.A. Youssef, Radiat. Phys. Chem. 55 (1999) 447. [179] M. Kim, K. Saito, Radiat. Phys. Chem. 57 (2000) 167. [180] El-S.A. Hegazy, H.A. Abd El-Rehim, A.M.I. Ali, H.G. Nowier, H.F. Aly, Nucl. Instr. and Meth. B 151 (1999) 393. [181] El-S.A. Hegazy, H.A. Abd El-Rehim, H.A. Shawky, Radiat. Phys. Chem. 57 (2000) 85. [182] El-S.M. Abdel-Bary, E.M. El-Nesr, Radiat. Phys. Chem. 48 (1996) 689. [183] N.H. Taher, A.M. Dessuoki, M.B. El-Arnaouty, Radiat. Phys. Chem. 53 (1998) 437. [184] N. Kabay, A. Katakai, T. Sugo, Radiat. Phys. Chem. 46 (1995) 833. [185] S.H. Choi, Y.C. Nho, Radiat. Phys. Chem. 58 (2000) 157. [186] T. Kawai, K. Saito, K. Sugita, T. Kawakami, J. Kanno, A. Katakai, N. Seko, T. Sugo, Radiat. Phys. Chem. 59 (2000) 405. [187] El-S.A. Hegazy, H.A. Abd El-Rehim, H. Kamal, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [188] S. Choi, S. Kim, E. Ryu, K-P. Lee, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [189] A.S. Homan, Adv. Polym. Sci. 57 (1984) 141. [190] M. Carenza, S. Lora, G. Palma, G. Pezzin, P. Caliceti, Radiat. Phys. Chem. 48 (1996) 231. [191] J. Chen, Y.C. Nho, O.H. Kwon, A.S. Homan, Radiat. Phys. Chem. 55 (1997) 87. [192] M.C. Port-Durrieu, C. Aymes-Chodur, C. Vergne, N. e Betz, C. Baquey, Nucl. Instr. and Meth. B 151 (1999) 404. [193] F. Yue-E, Z. Zia, G. Xuewu, S. Tianyi, Radiat. Phys. Chem. 49 (1997) 589. [194] R. Bagheri, F. Naimian, N. Sheikh, Radiat. Phys. Chem. 49 (1997) 497. [195] V. Haddadi-Asl, R.P. Burford, Radiat. Phys. Chem. 47 (1996) 907. [196] V.N. Kudryavtsev, L.E. Starannikova, V.V. Teplyakov, V.Y. Kabanov, Nucl. Instr. and Meth. B 151 (1999) 399. [197] I. Legocka, Z. Zimek, A. Woniak, Radiat. Phys. Chem. 52 (1998) 277. [198] G. Burillo, M.A. Oseguera, C. Vazquez, L.F. Del Castillo, Radiat. Phys. Chem. 50 (1997) 511. [199] E. Bucio, R. Aliev, G. Burillo, Presented at the Fourth International Symposium on Ionizing Radiation and polymers, 2428 September 2000. [200] I. Legocka, Z. Zimek, K. Mirkowski, A. Nowicki, Radiat. Phys. Chem. 57 (2000) 411. [201] H. Guanglin, W. Jie, Radiat. Phys. Chem. 42 (1993) 61. [202] V. Haddadi-Asl, R.P. Burford, J.L. Garnett, Radiat. Phys. Chem. 45 (1995) 191. [203] J.L. Garnett, L.T. Ng, V. Viengkhou, I.W. Hennessy, E.F. Zilic, Radiat. Phys. Chem. 57 (2000) 355.
29
[204] J. Garnett, L-T. Ng, D. Nguyen, V. Viengkhou, E. Zilic, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [205] R. DeGregorio, G. Filardo, A. Galia, F. Scr , G. Spadaro, o Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [206] M.C. Porte-Durrieu, C. Aymes-Chodur, N. Betz, B. Brouillaud, F. Rouais, A. Le Mol, C. Baquey, Nucl. e Instr. and Meth. B 131 (1997) 364. [207] C. Aymes-Chodur, N. Betz, M.C. Porte-Durrieu, C. Baquey, A. Le Mol, Nucl. Instr. and Meth. B 151 e (1999) 377. [208] V.V. Shirkova, I.P. Chihacheva, A.M. Evtushenko, S. Budris, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [209] J.M. Rosiak, in: R.L. Clough, S. Shalaby (Eds.), Radiation Eects on Polymers, American Chemical Society books, Washington, DC, 1991, p. 271. [210] J.M. Rosiak, P. Ula ski, L.A. Pajewski, F. Yoshii, K. n Makuuchi, Radiat. Phys. Chem. 46 (1995) 161. [211] A. Chapiro, Radiat. Phys. Chem. 46 (1995) 159. [212] I. Kaetsu, A. Singh, Radiat. Phys. Chem. 55 (1999) 111. [213] N.A. Peppas, Hydrogels in Medicine and Pharmacy, CRC Press, Boca Raton, 1986. [214] O. G ven, M. Sen, E. Karada, D. Saraydin, Radiat. Phys. u g Chem. 56 (1999) 381. [215] A.B. Lug~o, L.D.B. Machado, L.F. Miranda, M.R. a Alvarez, J.M. Rosiak, Radiat. Phys. Chem. 52 (1998) 319. [216] O.Z. Higa, S.O. Rogero, L.D.B. Machado, M.B. Mathor, A.B. Lug~o, Radiat. Phys. Chem. 55 (1999) 705. a [217] F. Yoshii, Y. Zhanshan, K. Isobe, K. Shinozaki, K. Makuuchi, Radiat. Phys. Chem. 55 (1999) 133. [218] J.M. Rosiak, P. Ulaski, Radiat. Phys. Chem. 55 (1999) 139. [219] S. Kiatkamjornwong, P. Suwanmala, Radiat. Phys. Chem. 52 (1998) 217. [220] L.C. Loprgolo, L.H. Catalani, L.D.B. Machado, P.R. e Rela, A.B. Lug~o, Radiat. Phys. Chem. 57 (2000) 451. a [221] A. Paparella, K. Park, in: R.L. Clough, S. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, American Chemical Society books, Washington, DC, 1996, p. 180. [222] Y. Aso, S. Yoshioka, Y. Nakai, S. Kojima, Radiat. Phys. Chem. 55 (1999) 179. [223] P. Ulaski, I. Janik, J.M. Rosiak, Radiat. Phys. Chem. 52 n (1998) 289. [224] O. Kantolu, M. Sen, O. Gven, Nucl. Instr. and Meth. B g u 151 (1999) 218. [225] H. Bodugz, N. Pekel, O. Gven, Radiat. Phys. Chem. 55 o u (1999) 667. [226] N. Pekel, N. Sahiner, O. Guven, Radiat. Phys. Chem. 59 (2000) 485. [227] S. Duran, D. Solpan, O. G ven, Nucl. Instr. and Meth. B u 151 (1999) 196. [228] H. T mtrk, T. Caykara, O. Kantolu, O. Gven, Nucl. u u g u Instr. and Meth. B 151 (1999) 238.
30
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [257] R.L. Clough, G.M. Malone, K.T. Gillen, J.S. Wallace, M.B. Sinclair, Polym. Degrad. Stab. 49 (1995) 305. [258] J.S. Wallace, M.B. Sinclair, K.T. Gillen, R.L. Clough, Radiat. Phys. Chem. 41 (1993) 85. [259] R.L. Clough, K.T. Gillen, G.M. Malone, J.S. Wallace, Radiat. Phys. Chem. 48 (1996) 583. [260] T.S. Dunn, E.E. Williams, J.L. Williams, J. Polym. Sci. 20 (1982) 1599. [261] J.L. Williams, E.E. Dunn, T.S. Dunn, J. Appl. Polym. Sci. 27 (1982) 951. [262] J.L. Williams, E.E. Williams, T.S. Dunn, Radiat. Phys. Chem. 19 (1982) 189. [263] J.L. Williams, T.S. Dunn, V.T. Stannett, Radiat. Phys. Chem. 19 (1982) 291. [264] J.L. Williams, in: A. Singh, J. Silverman (Eds.), Radiation Processing of Polymers, Oxford University Press, New York, 1992. [265] A. Shamshad, A.A. Basfar, Radiat. Phys. Chem. 57 (2000) 447. [266] J. Wise, K.T. Gillen, R.L. Clough, Polym. Degrad. Stab. 49 (1995) 403. [267] R.L. Clough, K.T. Gillen, in: J. Pospsil, P.P. Klemchuk (Eds.), Oxidation Inhibition in Organic Materials, CRC Press, Boca Raton, 1992, p. 191. [268] R.L. Clough, K.T. Gillen, M. Dole, in: D.W. Clegg, A.A. Collyer (Eds.), Irradiation Eects on Polymers, Elsevier, New York, 1991, p. 79. [269] R.M. Streicher, Radiat. Phys. Chem. 46 (1995) 893. [270] M.S. Jahan, K.S. McKinny, Nucl. Instr. and Meth. B 151 (1999) 207. [271] R. Buchalla, C. Schttler, K.W. Bgl, Radiat. Phys. Chem. u o 46 (1995) 579. [272] M. Deng, R.A. Johnson, R.A. Latour Jr., S.W. Shalaby, in: R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, ACS books, Washington, DC, 1996, p. 293. [273] J.V. Hamilton, M.B. Schmidt, K.W. Greer, C. Shah, Radiat. Phys. Chem. 52 (1998) 283. [274] P. Sinco, Nuclear News 43 (2000) 38. [275] A. Egan, J. Mardian, M. Foot, E. King, A. Millington, M. Nevin, C. Butler, J. Barker, D. Fletcher, Radiat. Phys. Chem. 46 (1995) 1303. [276] T. Czvikovszky, in: A. Singh, J. Silverman (Eds.), Radiation Processing of Polymers, Oxford University Press, New York, 1992, p. 121. [277] D. Solpan, O. G ven, Radiat Phys. Chem. 54 (1999) 583. u [278] J.L. Garnett, L.T. Ng, Radiat. Phys. Chem. 48 (1996) 217. [279] L.T. Ng, J.L. Garnett, S. Mohajerani, Radiat. Phys. Chem. 55 (1999) 633. [280] M. Khan, K. Ali, Radiat. Phys. Chem. 42 (1993) 167. [281] T. Czvikovszky, Radiat. Phys. Chem. 47 (1996) 425. [282] T.M. Stepanik, D.E. Ewing, R. Whitehouse, Radiat. Phys. Chem. 57 (2000) 377. [283] T.M. Stepanik, S. Rajagopal, D. Ewing, R. Whitehouse, Radiat. Phys. Chem. 52 (1998) 505. [284] J. Laine, E. Haukkovaara, P. Oraviita, P. Peltola, K. Oy, Lenzinger Berichte 62 (1987) 54.
[229] A.S. Homan, MRS Bulletin XVI (9) (1991) 42. [230] A.S. Homan, Macromol. Symp. 98 (1995) 645. [231] J. Chen, L. Yang, M. Wu, Q. Xi, S. He, Y. Li, Y.C. Nho, Radiat. Phys. Chem. 59 (2000) 313. [232] A. Safrany, Nucl. Instr. and Meth. B 131 (1997) 376. [233] L. Xuequan, Z. Maolin, L. Jiuqiang, H. Hongfei, Radiat. Phys. Chem. 57 (2000) 477. [234] A. Panda, S.B. Manohar, S. Sabharwal, Y.K. Bhardwaj, A.B. Majali, Radiat. Phys. Chem. 58 (2000) 101. [235] A.S. Homan, A. Afrassiabi, I.C. Dong, J. Control. Rel. 4 (1986) 213. [236] M. Negishi, A. Hiroki, M. Miyajima, M. Yoshida, M. Asano, R. Katakai, Radiat. Phys. Chem. 55 (1999) 167. [237] I. Kaetsu, K. Uchida, Y. Morita, M. Okubo, Radiat. Phys. Chem. 40 (1992) 157. [238] M. Sen, O. Gven, Radiat. Phys. Chem. 55 (1999) 113. u [239] F. Martellini, O.Z. Higa, E. Takacs, A. Safranj, M. Yoshida, R. Katakai, M. Carenza, Radiat. Phys. Chem. 55 (1999) 185. [240] Z. Maolin, L. Ning, L. Jun, Y. Min, L. Jiuqiang, H. Hongfei, Radiat. Phys. Chem. 57 (2000) 481. [241] W. Minghong, B. Bao, J. Chen, Y. Xu, S. Zhou, Z. Ma, Radiat. Phys. Chem. 56 (1999) 341. [242] M. Yoshida, M. Asano, T. Suwa, R. Katakai, Radiat. Phys Chem. 55 (1999) 677. [243] I. Kaetsu, Y. Morita, A. Otori, Y. Naka, Artif. Organs 14 (1990) 237. [244] M. Miyajima, M. Yoshida, H. Sato, H. Omichi, R. Katakai, W.I. Higuchi, Radiat. Phys. Chem. 46 (1995) 199. [245] I. Kaetsu, Radiat. Phys. Chem. 46 (1995) 247. [246] M. Carenza, P. Caliceti, F.M. Veronese, F. Martellini, O.Z. Higa, M. Yoshida, R. Katakai, Radiat. Phys. Chem. 57 (2000) 471. [247] H. Ichijo, O. Hirasa, R. Kishi, M. Oowada, K. Sahara, E. Kokufuta, S. Kohno, Radiat. Phys. Chem. 46 (1995) 185. [248] I. Kaetsu, K. Uchida, K. Sutani, S. Sakata, Radiat. Phys. Chem. 57 (2000) 465. [249] T. Descamps, Radiat. Phys. Chem. 46 (1995) 439. [250] K.J.L. Burg, S.W. Shalaby, in: R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, ACS books, Washington, DC, 1996, p. 240. [251] S.W. Shalaby, C.L. Linden Jr., in: R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, ACS Books, Washington, DC, 1996, p. 246. [252] D.A. Bedward, R.M. Brinston, J. Kotler, Radiat. Phys. Chem. 46 (1995) 443. [253] N. Harrison, in: D.W. Clegg, A.A. Collyer (Eds.), Irradiation Eects on Polymers, Elsevier, New York, 1991, p. 319. [254] L. Desch^nes, A. Arbour, F. Brunet, M.A. Court, G.J. e Doyon, J. Fortin, N. Rodrigue, Radiat. Phys. Chem. 46 (1995) 805. [255] M. Pentimalli, P. Ragni, G. Righini, D. Capitani, Radiat. Phys. Chem. 57 (2000) 385. [256] J. Gehring, Radiat. Phys. Chem. 46 (1995) 617.
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [285] D. Sandstrom, Svensk Papperstidn. 99 (1996) 27. [286] S. Rajagopal, T. Stepanik, Lenzinger Berichte 76 (1997) 37. [287] E. Takcs, L. Wojnrovits, C. F ldvry, P. Hargittai, J. a a o a Borsa, I. Saj, Radiat. Phys. Chem. 57 (2000) 399. o [288] E. Takcs, L. Wojnrovits, J. Borsa, C. Fldvry, P. a a o a Hargittai, O. Z ld, Radiat. Phys. Chem. 55 (1999) 663. o [289] M. Moharram, N. Abdel-Hakeem, S. Hammad, O. Mahmoud, Polym. Degrad. Stab. 39 (1993) 1. [290] Z. Ghazali, B. Wongsuban, K. Muhammad, K.Z. Dahlan, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [291] A. Olivier, F. Cazaux, C. Gors, X. Coqueret, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [292] G.S. Chauhan, S.K. Dhiman, L.K. Guleria, B.N. Misra, I. Kaur, Radiat. Phys. Chem. 58 (2000) 181. [293] S. Hassanpour, Radiat. Phys. Chem. 55 (1999) 41. [294] H. Hongfei, W. Liju, T. Hong, Z. Zhengguo, W. Jinshan, W. Jilan, Radiat. Phys. Chem. 46 (1995) 823. [295] S. Kiatkamjornwong, N. Meechai, Radiat. Phys. Chem. 49 (1997) 689. [296] G.F. Fanta, R.C. Burr, W.M. Doane, J. Appl. Polym. Sci. 24 (1979) 2015. [297] S. Kiakamjornwong, W. Chomsaksakul, M. Sonsuk, Radiat. Phys. Chem. 59 (2000) 413. [298] S. Choi, J. Seo, K. Lee, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [299] M.R. Al-Masri, K.D. Guenther, Radiat. Phys. Chem. 55 (1999) 323. [300] M. Lacroix, M. Jobin, E. Mezgheni, M. Srour, S. Boileau, Radiat. Phys. Chem. 52 (1998) 223. [301] E. Mezgheni, C. Vachon, M. Lacroix, Radiat. Phys. Chem. 58 (2000) 203. [302] D. Brault, G. D'Aprano, M. Lacroix, J. Agric. Food Chem. 45 (1997) 2964. [303] E. Mezgheni, G. D'Aprano, M. Lacroix, J. Agric. Food Chem. 46 (1998) 318. [304] M. Ressouany, C. Vachon, M. Lacroix, J. Agric. Food Chem. 46 (1998) 1618. [305] P.M. Subramanian, Resources, Conservation and Recycling 28 (2000) 253. [306] G. Burillo, R. Clough, T. Czvikovszky, O. Guven, A. Le Moel, W. Liu, A. Singh, J. Yang, T. Zaharescu, Radiat. Phys. Chem., submitted. [307] E. Adem, M. Avalos-Borja, D. Carrillo, M. Vazquez, E. Sanchez, M.P. Carreon, G. Burillo, Radiat. Phys. Chem. 52 (1998) 171. [308] J.C.M. Suarez, E.B. Mano, R.A. Pereira, Polym. Degrad. Stab. 69 (2000) 217. [309] J.C.M. Suarez, E.B. Mano, C.M.C. Bonelli, Polym. Eng. Sci. 39 (1999) 1398. [310] O. Revyakin, J. Zicans, M. Kalnins, V. Kalkis, Polym. Recycling 4 (1999) 33. [311] G. Burillo, P. Herrera, S. Martinez, M. Vazquez, E. Adem, Work presented at the IAEA Consultant's Meeting, Gifsur-Yvette, France, 1921 September 2000.
31
[312] Y. Fujii, M. Nomura, Bull. Res. Lab. Nucl. Reactor 20 (1996) 72. [313] G. Burillo, M. Galicia, M.P. Carreon, M. Vazquez, E. Adem, Radiat. Phys. Chem. 60 (2001) 73. [314] T. Czvikovszky, H. Hargitai, I. Rcz, G. Csukat, Nucl. a Instr. and Meth. B 151 (1999) 190. [315] T. Czvikovszky, H. Hargitai, Radiat. Phys. Chem. 55 (1999) 727. [316] T. Czvikovszky, H. Hargitai, Nucl. Instr. and Meth. B 131 (1997) 300. [317] T. Czvikovszky, Radiat. Phys. Chem. 47 (1996) 425. [318] T. Czvikovsky, Nucl. Instr. and Meth. B 105 (1995) 233. [319] J. Yang, in: W.J. Cooper, R.D. Curry, K.E. O'Shea (Eds.), Environmental Applications of Ionizing Radiation, Wiley, New York, 1998, p. 601. [320] W. Zhao, S. Hasegawa, J. Fujita, F. Yoshii, T. Sasaki, K. Makuuchi, J. Sun, S. Nishimoto, Polym. Degrad. Stab. 53 (1996) 199. [321] R.L. Clough, K.T. Gillen, Radiat. Phys. Chem. 18 (1981) 661. [322] Y.I. Matusevich, L.P. Krul, High Energy Chem. 33 (1999) 72. [323] Y.I. Matusevich, A. Polikarpov, L.P. Krul, High Energy Chem. 33 (1999) 224. [324] T. Seguchi, N. Kasai, K. Okamura, in: Proceedings of the Fourth International Symposium on Advanced Nuclear Energy Research, Mito, Japan, 57 February 1992, p. 62. [325] M. Takeda, Y. Imai, H. Ichikawa, T. Ishikawa, N. Kasai, T. Seguchi, K. Okamura, Ceram. Eng. Sci. Proc. 13 (1992) 209. [326] S. Kamimura, T. Seguchi, K. Okamura, Radiat. Phys. Chem. 54 (1999) 575. [327] S.R. Kurtz, C. Arnold Jr., J. Appl. Phys. 57 (1985) 2532. [328] A. De Bonis, A. Bearzotti, G. Marletta, Nucl. Instr. and Meth. B 151 (1999) 101. [329] F.F. Komarov, A.V. Leontyev, V.V. Grigoryev, Nucl. Instr. and Meth. B 166167 (2000) 650. [330] T. Terai, T. Kobayashi, Nucl. Instr. and Meth. B 166167 (2000) 627. [331] V.B. Odzhaev, V.N. Popik, E.I. Kozlova, O.N. Jankovskij, I.A. Karpovich, Nucl. Instr. and Meth. B 166167 (2000) 655. [332] K. Dworecki, T. Hasegawa, K. Sudlitz, S. Wsik, Nucl. Instr. and Meth. B 166167 (2000) 646. [333] Y. Wu, T. Zhang, H. Zhang, X. Zhang, Z. Deng, G. Zhou, Nucl. Instr. and Meth. B 169 (2000) 89. [334] I. Ercan, I. Gnal, O. Gven, Radiat. Phys. Chem. 46 u u (1995) 813. [335] M. Wolszczak, J. Kroh, M.M. Abdel-Hamid, Radiat. Phys. Chem. 45 (1995) 71. [336] U.A. Sevil, O. G ven, O. Birer, S. Suzer, Synth. Met. 110 u (2000) 175. [337] V.N. Popok, I.A. Karpovich, V.B. Odzhaev, D.V. Sviridov, Nucl. Instr. and Meth. B 148 (1999) 1106. [338] H. Ogiso, T. Ishida, W. Mizutani, S. Nakano, H. Tokumoto, Nucl. Instr. and Meth. B 148 (1999) 1097.
32
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [358] H. Omichi, M. Yoshida, M. Asano, N. Nagaoka, H. Kubota, R. Katakai, R. Spohr, N. Reber, A. Wolf, G.M. Alder, V. Ang, C.L. Bashford, C.A. Pasternak, Nucl. Instr. and Meth. B 131 (1997) 350. [359] M. Yoshida, N. Nagaoka, M. Asano, H. Omichi, H. Kubota, K. Ogura, J. Vetter, R. Spohr, R. Katakai, Nucl. Instr. and Meth. B 122 (1997) 39. [360] N. Reber, H. Omichi, R. Spohr, M. Tamada, A. Wolf, M. Yoshida, Nucl. Instr. and Meth. B 105 (1995) 275. [361] E. Ferain, R. Legras, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [362] L. Piraux, S. Dubois, S. Demoustier-Champagne, Nucl. Instr. and Meth. B 131 (1997) 357. [363] V.I. Yarygin, V.S. Mironov, N.P. Solovyev, O.V. Kolninov, V.V. Kolesnikova, A.I. Chernyavsky, A.S. Smolyansky, Nucl. Instr. and Meth. B 185 (2001) 228. [364] R.A. Pethrick, in: D.W. Clegg, A.A. Collyer (Eds.), Irradiation Eects on Polymers, Elsevier, New York, 1991, p. 383. [365] A.E. Novembre, N. Munzel, Microelectron. Eng. 32 (1996) 229. [366] H. Ito, G. Breyta, D. Hofer, A. Pomerene, K. Petrillo, D. Seeger, in: R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, ACS books, Washington, DC, 1996, p. 387. [367] D. Wheeler, E. Scharrer, G. Kubiak, R. Hutton, S. Stein, R. Cirelli, F. Baiocchi, M. Cheng, C. Boyce, G. Taylor, in: R.L. Clough, S.W. Shalaby (Eds.), Irradiation of Polymers: Fundamentals and Technological Applications, ACS books, Washington, DC, 1996, p. 399. [368] G.E. Moore, SPIE Proc. vol. 2440 (1995) 2. [369] L.F. Thompson, in: L.F. Thompson, C.G. Willson, M.J. Bowden (Eds.), Introduction to Microlithography, ACS books, Washington, DC, 1994, p. 1. [370] S.D. Berger, J.M. Gibson, Appl. Phys. Lett. 57 (1990) 153. [371] L.R. Harriott, S.D. Berger, C. Biddick, M. Blakey, S. Bowler, K. Brady, R. Camarda, W. Connelly, A. Crorken, J. Custy, R. DeMarco, R.C. Farrow, J.A. Felker, L. Fetter, L.C. Hopkins, H.A. Huggins, C.S. Knurek, J.S. Kraus, R. Freeman, J.A. Lidle, M.M. Mkrtchyan, A.E. Novembre, M.L. Peabody, R.G. Tarascon, H.H. Wade, W.K. Waskiewicz, G.P. Watson, K.S. Wereder, D.L. Windt, J. Vac. Sci. Technol. B 14 (1996) 3825. [372] G.D. Kubiak, D.A. Tichenor, M.E. Malinowski, R.H. Stulen, S.J. Haney, K.W. Berger, L.A. Brown, J.E. Bjorkholm, R.R. Freeman, W.M. Manseld, D.M. Tennant, O.R. Wood II, J. Bokor, T.E. Jewell, D.L. Windt, W.K. Waskiewicz, J. Vac. Sci. Technol. B 9 (1991) 3184. [373] K.B. Nguyen, G.F. Cardinale, D.A. Tichenor, G.D. Kubiak, K. Berger, A.K. Ray-Chaudhuri, Y. Perras, S.J. Haney, R. Nissen, K. Krenz, R.H. Stulen, H. Fukioka, C. Hu, J. Bokor, D.M. Tennant, L.A. Fetter, J. Vac. Sci. Technol. B 14 (1996) 4188. [374] T. Asmus, G.K. Wolf, Nucl. Instr. and Meth. B 166167 (2000) 732.
[339] Q.M. Zhang, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [340] R.G. Kammer, Materials Science and Engineering Laboratory Polymers: 1999 Programs and Accomplishments, National Institute of Standards and Technology, 2000. [341] P. Apel, A. Schulz, R. Spohr, C. Trautmann, V. Vutsadakis, Nucl. Instr. and Meth. B 146 (1998) 468. [342] P.Yu. Apel, I.V. Blonskaya, V.R. Oganessian, O.L. Orelovitch, C. Trautmann, Nucl. Instr. and Meth. B 185 (2001) 216. [343] A.A. Machula, T.E. Laricheva, S.M. Merkov, V.K. Milinchuk, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 428 September 2000. [344] D.L. Zagorski, A.I. Vilensky, A.L. Tolstichina, R.V. Gainutdinov, B.V. Mchedlishvili, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [345] G.S. Zhdanov, A.V. Bogacheva, V.K. Milinchuk, B.I. Belousov, A.B. Belousov, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [346] A.S. Smolyanskii, O.S. Zvezdina, V.G. Plotnikov, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [347] E. Ferain, R. Legras, Nucl. Instr. and Meth. B 131 (1997) 97. [348] C.A. Pasternak, G.M. Alder, P.Y. Apel, C.L. Bashford, Y.E. Korchev, A.A. Lev, T.K. Rostovtseva, N.I. Zhitariuk, Nucl. Instr. and Meth. B 105 (1995) 332. [349] L. Piraux, J.M. George, J.F. Despres, C. Leroy, E. Ferain, R. Legras, K. Ounadjela, A. Fert, Appl. Phys. Lett. 65 (1994) 2484. [350] A. Blondel, J.P. Meier, B. Doudin, J.P. Ansermet, Appl. Phys. Lett. 65 (1994) 3019. [351] K. Liu, K. Nagodawithana, P.C. Searson, C.L. Chien, Phys. Rev. B 51 (1995) 7381. [352] M.E. Toimil Molares, J. Brtz, V. Buschmann, D. o Dobrev, R. Neumann, R. Scholz, I.U. Schuchert, C. Trautmann, J. Vetter, Nucl. Instr. and Meth. B 185 (2001) 192. [353] N. Reber, H. Omichi, R. Spohr, A. Wolf, M. Yoshida, Nucl. Instr. and Meth. B 151 (1999) 146. [354] D. Paul, Presented at the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [355] S.K. Chakarvarti, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [356] S.N. Dmitriev, L.I. Kravets, V.V. Sleptsov, V.M. Elinson, Abstract submitted to the Fourth International Symposium on Ionizing Radiation and Polymers, 2428 September 2000. [357] N.I. Shtanko, V.Y. Kabanov, P.Y. Apel, M. Yoshida, Nucl. Instr. and Meth. B 151 (1999) 416.
R.L. Clough / Nucl. Instr. and Meth. in Phys. Res. B 185 (2001) 833 [375] E.W. Becker, W. Ehrfeld, P. Hagmann, A. Maner, D. Mnchmeyer, Microelectron. Eng. 4 (1986) 35. u [376] W. Ehrfeld, H. Lehr, Radiat. Phys. Chem. 45 (1995) 349. [377] H. Guckel, K.J. Skrobis, J. Klein, T.R. Christenson, J. Vac. Sci. Technol. A 12 (1994) 2559. [378] E.J. Garcia, J.J. Sniegowski, Sensors and Actuators A 48 (1995) 203. [379] S.V. Springham, T. Osipowicz, J.L. Sanchez, L.H. Gan, F. Watt, Nucl. Instr. and Meth. B 130 (1997) 155.
33
[380] J.L. Sanchez, J.A. van Kan, T. Osipowicz, S.V. Springham, F. Watt, Nucl. Instr. and Meth. B 136138 (1998) 385. [381] J.A. van Kan, J.L. Sanchez, B. Xu, T. Osipowicz, F. Watt, Nucl. Instr. and Meth. B 148 (1999) 1085. [382] D.M. Rck, Nucl. Instr. and Meth. B 166167 (2000) 602. u [383] D.M. Rck, J. Schulz, N. Deusch, Nucl. Instr. and Meth. u B 131 (1997) 149. [384] P. Cottin, R.A. Lessard, E.J. Knystautas, S. Roorda, Nucl. Instr. and Meth. B 151 (1999) 97.

High Energy Radiation and Polymers, A Review of Commercial Processes and Emerging Applications

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

High Energy Radiation and Polymers, A Review of Commercial Processes and Emerging Applications

Uploaded by

Copyright:

Available Formats

Nuclear Instruments and Methods in Physics Research B 185 (2001) 833

Tel.: +1-505-844-3492; fax: +1-505-844-9624. E-mail address: rlcloug@sandia.gov (R.L. Clough).

0168-583X/01/$ - see front matter Published by Elsevier Science B.V. PII: S 0 1 6 8 - 5 8 3 X ( 0 1 ) 0 0 9 6 6 - 1

You might also like