ADVANCED POLYMER COMPOSITES FOR THE FABRICATION OF SPENT NUCLEAR FUEL DISPOSAL CONTAINERS

HUGUES W. BONIN,* IAN MIEDEMA, and VAN TAM BUI

Royal Military College of Canada, Department of Chemistry and Chemical Engineering P.O. Box 17000, Station FORCES, Kingston, Ontario K7K 7B4, Canada

MATERIALS FOR NUCLEAR SYSTEMS KEYWORDS: spent nuclear fuel, disposal containers, polymer composites

Received July 11, 2007 Accepted for Publication February 27, 2008

In Canada, the spent nuclear fuel disposal method proposed is to permanently isolate the spent fuel in deep underground vaults carved in stable granite rock formations within the Canadian Shield, with the integrity of the isolation to be assured for a minimum period of 500 yr. The present work aims at determining the feasibility of using a consolidated composite material made of an advanced polymer called PEEK (Poly Ether Ether Ketone) and continuous graphite fiber to fabricate a container designed to isolate the spent nuclear fuel from the biosphere for such very long time periods. The research focused on submitting the PEEK-based composite material to a thermal and radioactive environment comparable to, and, in some aspects, more aggressive than, the conditions of exposure in the disposal vault. The changes to the physical, mechanical, and chemical properties of the material following prolonged exposure were then de-

termined. The simulation of the environment was achieved by irradiating numerous test specimens in a mixed radiation field produced by a SLOWPOKE-2 nuclear research reactor at controlled ambient temperatures ranging from ;20 to 758C. The specimens were characterized via several methods: tensile and flexural testing, differential scanning calorimetry, scanning electron microscopy, and wide-angle X-ray scattering. The results confirmed that the PEEK-based composite material was resistant to exposure to high radiation doses (1 MGy), at temperatures between ;20 and 758C. The mechanical and other properties were barely affected, with values rarely exceeding 1s of the properties of nonirradiated samples, suggesting that the PEEKgraphite fiber composite material can indeed be considered as a very good candidate for this demanding application.

I. INTRODUCTION The issue of the ultimate disposal of spent nuclear fuel and high-level radioactive waste is of paramount importance for the success of nuclear energy as a major reliable, safe, and environmentally benign source of electrical power. Since some of the radioisotopes present in the spent nuclear fuel need several centuries for their radioactivity to decay back to background levels, the problem consists of not only protecting the present generation of humans and living beings from the hazards caused by the radiation but also isolating the radioactive
*E-mail: bonin-h@rmc.ca 286

waste from future generations for the following several centuries. The fuel element ~called fuel bundle! currently used in Canada deuterium uranium ~CANDU! nuclear reactors consists of 37 natural uranium fuel rods grouped and welded together to end plates. In the Canadian approach for the spent fuel disposal, the fuel bundles remain intact as no reprocessing operations are carried out on them. They would then be simply stored in specially designed containers ~Fig. 1!, the current design proposed by Atomic Energy of Canada Limited 1,2 ~AECL! foreseeing a capacity of 72 bundles per container, which would be made of copper, although titanium alloys have been considered. The containers in turn are to be inserted in cavities carved in the floor and0or sides of galleries dug as an
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Fig. 1. Spent CANDU fuel disposal container as proposed by AECL ~Ref. 2!.

extensive network at a depth of some 500 to 1000 m in granite rock formations within the Canadian Shield geologic province. The selected rock formations are known as plutons and are huge monoliths that have survived intact the numerous geologic upheavals that have occurred during the last several billions of years. The deep underground approach for the spent nuclear fuel disposal, as proposed in Canada, is based on the assumption that no matter the barrier, given enough time, it is bound to fail. The design proposed by AECL is presented in Table I and Fig. 2. Since the time frame considered here is of the order of several centuries, the engineering effort aims at ensuring that when all the barriers have failed, the escaping radioisotopes would have decayed back to natural background levels by the time they manage to physically reach the biosphere. Each one of the barriers has a probability of failure that varies with time. The event consisting of the radioisotopes reaching the biosphere can occur only when all the barriers have failed simultaneously and the overall probability for this is equal to the product of the individual probabilities. Since the barriers are designed such that their probabilities of failure are much smaller than one, an extremely low probability of occurrence for the event is thus obtained. The approach proposed by AECL was recommended by the Nuclear Waste Management Organization ~NWMO! in its final study report,3 except that the NWMO recommended that a provision

TABLE I Multibarrier System* Nature of Barrier Main Function~s! Engineered ~Designed! Barriers Uranium dioxide fuel Zircaloy sheath Filler material ~glass beads! a Container walls Clay buffer Backfill Traps most of radioisotopes Contains the spent fuel radioisotopes; impedes or delays contact to groundwater Provides heat transfer medium Delays access to groundwater; contains radioisotopes Delays access to groundwater and migration of radioisotopes Delays migration of radioisotopes The Geosphere ~Selected! Plutonic rock Natural aquifers Impedes or delays migration of radioisotopes May disperse the radioisotopes The Surface Environment ~Biosphere! ~Out of Human Control! Surface water, plants, animals, air Disperses and dilutes the radioisotopes

*Reference 2. a Information above from Ref. 3. In the present work, thorium dioxide is proposed to replace glass beads as filler material in the container. In addition to improving the heat transfer, ThO 2 would serve as an excellent gamma radiation absorber to protect the container walls.
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Fig. 2. Multibarrier system: Vault.

for eventual retrieval of the spent nuclear fuel be included in the disposal concept. On June 14, 2007, the Minister of Natural Resources of Canada announced that the Government has accepted the approach recommended by NWMO ~Refs. 4 and 5!. II. CONTEXT AND GOALS OF THE RESEARCH Providing a solution to the issue of the permanent safe disposal of the spent nuclear fuel and radioactive waste will certainly help in improving the public acceptance of nuclear energy since this issue is one of the main arguments used by nuclear activists opposing the development of nuclear energy. The present work aims at providing a valuable contribution to the field of spent nuclear fuel management by focusing on the container housing the spent nuclear fuel bundles. The container represents one of the multiple barriers mentioned above. The reader
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must be aware that the present work is much more than a simple research on materials intended to determine how some materials behave after having been irradiated under specific conditions. The goal is to demonstrate that a polymer-based composite material can effectively be used instead of metals to fabricate the containers for the spent nuclear fuel disposal. The intent of the work is therefore focused on the application rather than on the material itself. The paper thus uses an extensive set of experimental data obtained and presents them in support of the applicability of the Poly Ether Ether Ketone ~PEEK! and continuous graphite fiber ~PEEK-GF! composite material to the container fabrication. In such a context, the length of the paper is thus well justified. The container must be fabricated with materials displaying exceptional performance such as high mechanical strength, resistance to radiation, and excellent chemical resistance. Because of the large number of containers required over the years, consideration must be given to the production costs, the environmental impact of the production, the availability of the materials, and the fabrication technology as well as transportation issues. The containers must keep their integrity under adverse conditions for at least 500 yr ~Ref. 2!. Some of the best materials meeting these requirements are a few metals such as copper and titanium, certain alloys based on these metals, and stainless steel. However, the main concern with all metals is corrosion. Even if several metals and alloys display very good resistance to corrosion for up to modest time ranges, it is not well known how these materials can withstand several centuries of exposure to aggressive environments such as found in the deep underground vaults in contact with alkaline or acidic groundwater while being bombarded by the radiation emitted by the spent nuclear fuel. Another factor present at the disposal site is the relatively elevated temperatures. The spent nuclear fuel continues to generate heat long after removal from the nuclear reactor core because of the energy released by residual fissions ~spontaneous and stimulated! and by the radioactive decay processes of the fission products. Even after extended dwelling periods in the spent fuel bays, the spent fuel bundles can still generate enough heat to bring the temperature of the container walls close to 1008C. In addition, the mechanical forces due to the hydrostatic pressure of the plutons granite at such depths must be accounted for. In its proposal,2 AECL suggests the use of the metals and alloys mentioned above to fabricate the disposal containers. These choices are based on the knowledge that copper artifacts have been found in a relatively good state of preservation in archaeological sites several centuries, millennia in some cases, after their fabrication. In the case of titanium-based alloys, they are known to display good resistance to aggressive corrosive agents, but the knowledge acquired through experimentation is only relatively recent, and doubts persist on their long-range resistance to corrosion.
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The present research therefore aims at providing sound answers to the following questions. Are there alternative materials to the metals for the fabrication of the spent nuclear fuel disposal containers? If yes, then what are the most promising materials? How does one know that these materials indeed meet the requirements for such a demanding application? Since decisions must be made on the selection of the materials for the fabrication of the disposal containers within the next decade or so, experimental work must be carried out over a realistic span of time and certainly much less than the required 500 yr in order to ascertain the perfect integrity of the container. Therefore, the present research aims at providing an acceptable answer to the following question: How does one design an experimental procedure for the simulation of the exposure over a minimum of 500 yr of the container material to the aggressive environment present at the disposal site deep underground? Previous studies 68 have shown that PEEK and PEEKbased composites display excellent radiation stability. No research has been previously reported on the combined effects of irradiation and elevated temperatures on PEEK composites. High temperatures enhance the mobility of the polymer chains and radiation-induced chemical radicals, affecting either the rate of chain scission or even the cross-linking rate by freer movement of the polymer backbones, thus affecting the physical, mechanical, and chemical properties of the irradiated material. In the present study, mechanical, chemical, and thermal properties of PEEK-based composites are investigated after exposing the composite material to a mixed radiation field at temperatures ranging from ;20 to 758C. From the information collected experimentally using a variety of analytical methods and tests, the research work thus aims at determining whether or not a PEEK-based composite represents a suitable alternative to metals and metallic alloys for the fabrication of spent nuclear fuel containers and, in the case of a positive conclusion, to which extent this composite may be even superior for such an application.

III. PEEK AND COMPOSITE MATERIALS The composite material investigated here is based on PEEK, also known as polyaryletheretherketone, in conjunction with continuous graphite fiber as reinforcing material ~PEEK-GF!. The polymer was first synthesized in the early 1980s, but because of its costs, it has not yet been used in many applications. Its chemical and mechanical properties are outstanding and well comparable to those of metals and alloys for the mechanical properties while the chemical resistance is much superior to that of the metals. While metals and metallic alloys undergo corrosion-type chemical degradation, by their nature, polymers do not experience corrosion. However, other types
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of chemical aggression may lead to the degradation of the material, but PEEK has proven itself to have a very high resistance to these chemical reactions.9 Another factor affecting polymers and metals is the effect of ionizing radiation such as gamma rays, highenergy electrons, and neutrons. Since the disposal container has to isolate the spent nuclear fuel for extended periods of time, the container walls have to accumulate significant doses of radiation. Because of their crystalline nature, metals display high resistance to the effects of radiation, while most polymers are much less resistant. However, PEEK and composite materials based on this polymer have proven themselves to be little affected by radiation because of their chemical structure based on multiple and unusually stable benzene-like structure and delocalized pi electrons.10 Figure 3 shows the basic structure of PEEK. The regularity and linearity of the mer structure and the lack of bulky groups are to be noted. The backbone of this polymer is especially rigid because of the dominant phenyl groups. The side groups and the regularity of the polymer provide it with a semicrystalline morphology.11 Polymers rarely completely crystallize, and most end up after curing with regions having a crystallized structure ~called crystallites! embedded in an amorphous matrix. Like their mineral and metallic counterparts, the crystallites have their molecules regularly arranged as repetitive cells, but in the case of polymers, these cells grow in an axial direction mostly and rarely in the other directions at the same time. This semicrystalline structure of PEEK, coupled with the presence of dominating phenyl functional groups along the polymeric chain, provides PEEK with exceptional resistance to radiation. The energy of the radiation is thus dissipated within the crystallites through a phenomenon known as the cage effect 12 and within the many aromatic structures of the phenyl groups, thus avoiding damaging the structure and the bonds of the molecules. It is thus the weakest bonds ~C-H and C-O! that are targeted generally by the ionizing radiation, leaving the aromatic rings and the ketone side groups essentially unaffected. In addition to the aromatic structures providing a multiple resonance effect, the presence of the delocalized pi electrons contributes to spreading the effects of the deposited energy throughout the whole structure.10 Delocalized pi electrons are electrons that are not solely within a given chemical bond. In benzene, the pi electrons constitute two identical electron clouds above and below

Fig. 3. Chemical structure of poly~oxy-1,4-phenyleneoxy-1,4phenylnecarbonyl-1,4-phenylene!. 289

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the plane of the aromatic ring. The delocalization effectively reduces the repulsive forces between the electrons and lowers the energy of the molecule thus making the individual bonds more difficult to ionize and enhancing the resistance of the molecule to ionizing radiation. A major concern, especially for polymer-based materials, is that of creep. This is a phenomenon common for most polymers submitted to high temperatures. It is known 13 that creep does not become an important factor in a polymer for temperatures below one-third of the melting temperature. In the case of PEEK, the melting temperature is 3438C, and therefore, creep is not expected to be important below one-third of this value, i.e., 1148C. The maximum value for the temperature of the container walls is predicted to be below 1008C, clearly below the critical value above which creep would represent a problem. The creep rate is therefore not retained among the properties investigated in this study.

IV. EFFECTS OF IONIZING RADIATION ON POLYMERS The types of ionizing radiation making the mixed radiation field to which the composite material is subjected in this work are the fast and thermal neutrons, X-rays and gamma photons, and charged particles ~protons and electrons!. Having no electrical charge, neutrons are not technically ionizing radiation, but they knock out other particles such as protons, which in turn travel at high velocities as positive ions thus becoming themselves highly effective ionizing agents. Charged particles traveling at high velocities within some material strip electrons from the atoms encountered, thereby ionizing them. The photons ~X-rays and gamma rays! also ionize the atoms with which they interact but through different mechanisms: Compton and photoelectric effects, and pair production. While this is true in any kind of material, the overall effects differ according to the type of material. In polymers and polymer-based composite materials, the creation of ions triggers series of chemical reactions as the ions themselves often become chemically active radicals. In these materials, the overall effects from the radiation are the occurrence of cross-linking and chain scission chemical reactions. Cross-linking is the recombination of adjacent polymer chains with bonds that link them to one another, resulting in higher-weight molecules and higher mechanical resistance. Quite differently, chain scission results in the division of long chains into smaller components when weaker bonds are broken either directly by the incident radiation or, more frequently, indirectly as a result of chemical attack by the free-moving radicals produced by the interaction with radiation. In this case, the mechanical strength of the material is lessened significantly. Depending on the ambient conditions, one type of reaction is predominant.
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These ambient conditions include the molecular structure, the crystallography, the reactive species created as a result of the interaction with the incident radiation, the freedom of movement of these species, the temperature, the ambient pH, and the accumulated radiation dose. This would determine whether the overall effects of the radiation will strengthen or weaken the material and will modify its physical and chemical properties in a favorable or baneful manner. Many studies have been carried out on the effects of radiation on PEEK and PEEK composites, with a focus on space applications since these materials are promising candidates for the fabrication of space vehicle components and would be exposed to demanding environments in which the bombardment by cosmic rays and high radiation fields in the Earths magnetosphere would be an important component. Yoda 14,15 exposed these materials to high-energy electron beams, while Hegazy et al.16,17 used both electrons and gamma radiation. In both studies, radiation effects tended to occur preferably in the amorphous region of the polymer rather than within the crystalline region, mostly evidenced by the cross-linking occurrence. A more recent investigation by Pag 6,8 focussed on the radiation-induced effects on PEEK when subjected to a mixed field of radiation produced by a small nuclear reactor. Both the materials morphology and viscoelasticity were studied in addition to other properties. Again, both cross-linking and chain scission were evidenced, with chain scission being the dominant factor in the polymers degradation, with the interface between the crystalline and amorphous regions being the most affected regions. When compared to the effects of electron radiation alone, the mixed field of radiation produced a more rapid degradation of the PEEK. Sasuga et al.1822 have also done several investigations on the radiolysis of PEEK, using gamma, electron, or ion radiation in various environments. Tensile testing and differential scanning calorimetry ~DSC! enabled them to assess the extent of modifications brought in the material by the radiation, observing the simultaneous occurrence of cross-linking and chain scission as the doses accumulate. The room temperature mechanical properties, as well as the high-temperature properties, were only very slightly affected by the radiation doses up to 180 MGy, with only a slight increase in mechanical properties due to cross-linking at the higher temperatures. As for the carbon fibers, Jones and Peggs 23 studied the effects of neutrons on the carbon fibers. Their investigation was conducted over a range of fluence and temperature from 4 10 17 n cm 2 at 4208C to 5.4 10 20 n cm 2 at 6658C. It was found that both the fracture strength and the elastic modulus tended to increase with larger radiation doses. These results were similar to those from tests done at much lower temperatures ~,808C! under similar fluences. The density and the crystallite size were also observed to increase. This was attributed to a recrystallization process during the irradiation.
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TABLE II Property Data for PEEK-GF Composite* Fiber Volume ~%! 53.0 Density ~g cm 3 ! 1.56 Processing Temperature ~8C! 371 to 391 Flexural Strength ~MPa! 944.6 Flexural Modulus ~MPa! 53.09

TABLE III Ionizing Particles Produced by SLOWPOKE-2, Steady-State Half-Power Operation at Reactor Midheight and at 32.0 cm from Core Centerline* Ionizing Particles Electrons Gamma photons Recoil protons Fast and thermal neutrons Total % 88.6 7.2 2.8 1.4 100

*Reference 24.

V. METHODOLOGY The PEEK-GF composite used in this work was obtained from Applied Fiber Systems, Clearwater, Florida, under the trade name of Towflex . It consists of woven continuous graphite fiber in a 2 2 twill using a matrix of Victrex Grade 150 PEEK. The composite was produced by stacking plies of woven fabric preimpregnated with PEEK resin powder and compression moulding into a consolidated sheet. The final property data are listed in Table II ~Ref. 24!. The PEEK-GP composite samples were initially cut from a 75-cm 2 panel into 2.54- 7.62-cm samples, themselves further cut into specimens of dimensions 1.27 7.62 0.32 cm using a liquid-cooled band saw. Figure 4 shows one of these samples of the composite material. The dark gray graphite fibers are clearly visible, with the PEEK matrix appearing as the light gray component. The samples of the PEEK-GF composite were first analyzed for purity using neutron activation analysis. The results showed that there were very few impurities, with only traces of calcium, sodium, titanium, zinc, and even gold detected. The SLOWPOKE-2 nuclear reactor at the Royal Military College of Canada ~RMC! is a 20-kW~thermal! inherently safe pool-type nuclear reactor that produces a broad-spectrum mixed radiation field. This research reactor was readily available for this work as a convenient

*References 25 and 26.

source of the mixed radiation field that included a neutron component in addition to major gamma-ray and electron components, quite similar to the actual radiation field emitted by the spent nuclear fuel but with a larger intensity. For this work, the SLOWPOKE-2 reactor was operated at half power because it served several other researchers simultaneously, most of them using neutron activation analysis and for which the reduced reactor power is more convenient. The PEEK-GF samples were positioned by an elevator device in the reactor pool at 32 cm from the core center line, against the outer side of the reactor vessel wall. Table III presents the results of the mixed radiation field obtained from a previous study,25,26 at this position and at half power. The corresponding total dose rate was determined to be 3.7 10 4 Gy h 1. While the previous study referenced above has attempted at determining energy spectra for the various particles composing the mixed field produced by the SLOWPOKE-2 nuclear reactor at the irradiation site, both experimental data and computer simulation codes did not produce energy spectra with reasonable accuracy. As it will be discussed below, the spectral effects of the particles have only a marginal importance in the context of the present work.

Fig. 4. PEEK-GF composite material ~with graphite fibers!.

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Fig. 5. Irradiation setup for the PEEK samples.

The irradiation of the samples took place in a specially designed heated chamber that was immersed in the pool of the SLOWPOKE-2 nuclear reactor and positioned against the reactor vessel with the midsections of the samples in line with the midplane of the reactor core, at 32 cm from the core center line and ;6-m depth. Figure 5 presents a photograph of the irradiation chamber at its irradiation position. The chamber is an acrylic box, open at the bottom to allow installation and removal of the sample holder and the samples. The system uses a carbon heater connected to aluminum terminals and wires and controlled through a Hewlett Packard 6264B DC variable 400-W direct-current ~dc! power supply. The chamber is fed by pressurized air at a rate set up to keep the pressures both inside and outside the chamber equalized, thus preventing pool water from entering the chamber. Table IV presents the irradiation and temperature combinations carried out. At the end of the irradiation period, the chamber containing the irradiated samples was moved away from the reactor vessel and positioned at midway up in the reactor pool at a position not reached by the neutrons emitted by the reactor. The samples were left there for a cooldown period in order to bring the radiation dose rate from the elevator components, the chambers materials, and the samples to values below the maximum permissible dose rate of 2.5 mSv h 1
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TABLE IV Irradiation Profile Irradiation Temperature ~8C! 13 to 15 ~Pool water temperature! Total Exposure ~h! 0 1 7 27 0 1 7 27 0 1 7 27 Accumulated Dose ~kGy! 0 37 259 999 0 37 259 999 0 37 259 999

50

75

~2.5 mrem h 1 ! at the surface of the chamber. This way, the samples were handled safely for subsequent analyses that included tensile and flexural testing, DSC, scanning electron microscopy ~SEM!, and wide-angle X-ray scattering ~WAXS!. All the tests were conducted
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on computer-controlled devices for a high level of accuracy, precision, and repeatability. The composite samples were tested as rectangular flexural samples using an Instron Model 4206 equipped with the Series IX Automated Materials Testing System Revision K. The data collection was done with an IBMcompatible computer system through an IEEE interface. ASTM International ~ASTM! Standard D 790, Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials, 27 was followed. The three-point bend test ~Test Method 1! was the test method followed. The length-tothickness ratio was 1601, with a support span of 50 mm ~measured to 61%!, and the crosshead speed was 1.3 mm min 1. Each specimen was measured for width and thickness to the nearest 0.03 mm at the center of the support span using a digital micrometer. For each run ~dose0temperature combination!, a total of six samples was tested, with the software reporting the properties with a mean and a standard deviation for all the samples within the run. Differential scanning calorimetry is a thermal method for measuring transitions in materials. In most applications, the transitions evidenced by the DSC method are the glass transition temperature Tg , the crystallization and recrystallization temperatures Tc and Trc , and the melting temperature Tm . In addition, the technique can provide information on the heat of crystallization and the heat of fusion for the materials investigated. For these analyses, a TA Instruments DSC 2010 apparatus was used in conjunction with an IBM-compatible Instrument Control V 2.5 operating system. The procedure followed ASTM Standards D 3418 ~Ref. 28! and D 3417 ~Ref. 29!. The PEEK-GF nonirradiated and irradiated samples were cut into pieces of ;10 mg and placed into sealed DSC pans, followed by a thermal relaxation period of ;10 min at 4008C, then quenched to 508C below the Tg ~being ;1458C!, and placed into the DSC chamber. For the Tg and Tc determination, the samples were heated at a rate of 208C min 1 until 2508C under a nitrogen atmosphere. For the measurements of Tm and Trc , the heating rate used was 108C min 1 until 4008C, held for 10 min, then cooled down at the same rate. All relevant data were recorded in the data acquisition system and sent as ACSII files for further analysis. Wide angle X-ray scattering is an analytical method using diffracted X-ray radiation to determine the crystalline structure of materials. Generally, the sample to be analyzed is irradiated by an X-ray beam at a certain angle, and the diffracted X-ray photons are detected via a detector that is swung around the sample through an angle 2u. The detector may consist basically of a flat photographic plate onto which the diffracted beam is projected or as a strip of film encircling the sample. In the first case, the diffracted beams are recorded as circles, and in the latter case, the beams appear as arcs. The detectors response is displayed as a plot of X-ray diffraction ~XRD!
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intensity versus 2u, called an XRD pattern. The higherintensity peaks indicate preferred diffraction angles and provide information on the type of crystals and their Miller indices. These well-defined peaks are due only to the crystalline portions of the materials studied. Amorphous substances yield only diffuse responses from the detector, known as an amorphous halo. In this work, the graphite fibers within the composite material are also detected by the method and produce a well-identifiable intensity plot, as is the case for the amorphous component of the composite material. The amount of crystallinity of the polymer can be quantitatively determined though the intensity-2u graph, via the integration of the XRD pattern, after the pattern has been split into three components: crystalline, amorphous, and Compton scattering. Using the Ruland 30 method, the volume fraction of crystallinity can be found. In semicrystalline polymers, the crystals are oriented randomly and, consequently, do not diffract into single points. To overcome this difficulty, the Debye-Scherrer method 31 is used for the analysis. The WAXS analysis was carried out using a Scintag diffractometer with a u-u geometry goniometer coupled with DMS2000 diffraction management system software. The samples used for this analysis were 2-cm-long pieces cut from the narrow section of the tensile samples to ensure that the same portion was tested for all other analysis techniques. There was one sample for WAXS analysis for each of the dose0temperature sample groups. The samples were scanned from 2u 2 to 40 deg at a rate of 1.8 deg min 1 and a step size of 0.03 deg. The X-rays were produced by a copper target, and their wavelength was 1.54 . Disregarding the carbon halo, the strongest peak observed was the 18.9-deg peak, which was used to determine the crystallite size. The final analytical method used in this work was SEM. The method essentially detects backscattered electrons from a small sample of the material in order to produce a greatly magnified image that can be visually analyzed. The specimens examined here are not electrically conductive, and for this technique to be applied successfully, their surface must be plated with a conducting material such as gold. This was done for this work using a Polaron SC7640 sputter coater with gold as plating material. The SEM apparatus used was a Phillip XL 30CP scanning electron microscope. Each sample was first cut to a length of ;1 cm and attached to an SEM anode stand. They were fixed to the stand with carbon glue and then gold plated. Then, they were placed inside the SEM vacuum chamber, and several images of them were taken with a variety of magnifications ~typically 20X, 29X, 42X, 482X, and 1017X!. VI. EXPERIMENTAL RESULTS The results of the mechanical testing for the samples for the PEEK-GF composite material are presented in
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Fig. 6. Typical load-extension graph for a PEEK-GF composite sample ~nonirradiated at reactor pool temperature!.

Figs. 6, 7, and 8. Figure 6 presents a typical loadextension graph, for a PEEK-GF 0DRT composite sample ~zero dose, room temperature!. The designation room temperature here is synonymous with pool temperature and indicates the temperature of the pool water surrounding the samples irradiation box near the bottom

of the reactor pool. Since the reactor pool water is in thermal equilibrium with both the reactor vessel and the outer wall of the pool itself in contact with the underground materials ~mostly limestone!, the pool temperature would then vary with the season and the power level of the reactor, from ;138C in the middle of the winter just before the reactor start-up early in the morning, to ;238C in summer with the reactor at full power. As shown by the results, any variations of the measured data caused

Fig. 7. Flexural strength of PEEK-GF composite material with respect to the duration of irradiation ~at half reactor power!, for the various temperatures investigated. 294

Fig. 8. Flexural modulus of PEEK-GF composite material with respect to the duration of irradiation ~at half reactor power!, for the various temperatures investigated.
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by the variation of the pool temperature are indeed minimal and well within the error bars. The curve in Fig. 6 is produced by the software of the Instron flexural testing apparatus, and its features are used for determining the final results such as the modulus. While it could have been preferable that the software produces a curve in terms of the strain instead of the extension, the purpose of inserting Fig. 6 here is to provide the reader with an example of intermediate results in order to help with the understanding of this part of the experimental work. The strain can be calculated from the extension. Since the flexural method is a well-known analytical technique, it is felt as appropriate in the present paper to limit the depth of the description of the method and invite the reader to consult the appropriate reference ~Ref. 26!. The curve in Fig. 6 displays the sharp breaking point that is typical of composites and brittle materials in general. The linear portion of the curve permits the determination of the rupture stress. Several further jagged breaking points are observed after the yield point: These represent the breaking of the fibers, thus indicating that the sample is no longer consolidated. The matrix and fibers work in unison to produce the high strength of the composite material, but once past the rupture point, these components must absorb the energy separately. With more ductile materials ~such as the virgin PEEK!, there is usually a flat linear portion of the load-extension curve following a local maximum, the flat portion ending abruptly at the break point. For the nonirradiated composite samples at room temperature, a flexural modulus of 49.7 6 1.1 GPa and a yield strength of 852 6 44 MPa are obtained, and these results are the basis for comparison with the results for irradiated samples. In the graphs depicted in Figs. 7 and 8, it is evident that the strength and modulus are only minimally affected by the radiation doses. For the composite samples, one observes a very slight drop following the initial radiation dose ~37 kGy! for each of the temperature subgroups. Such a decrease in the mechanical strength and modulus is indicative of the predominance of chain scission, an effect already known from previous experience with polymers.9 Figures 7 and 8 also provide information on the effects of the temperature of the samples during their irradiation in the pool of the SLOWPOKE-2 reactor. For the PEEK-GF composite material, higher temperatures tend to decrease the values of the flexural strength and modulus, but only slightly as the dose increases. In some cases, the effect is marginal at best. Since the thermal expansion coefficients are different for the graphite fibers and the PEEK matrix in the composite material, higher temperatures create additional stresses at the interface between the fibers and the matrix, thereby enhancing the chain scissions caused by the radiation. However, one should note that all the changes occur within the error bars such that from the accuracy of the results, it is not possible to come to a conclusion on whether these changes are real or not. If these are actual
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changes due to the combined effects of the radiation dose and the temperature, then the changes are minimal at best, but in the context of the present research, these results are indeed positive as they demonstrate that the PEEK-GF composite material can withstand the combined aggressive action of the radiations and the temperature. Figure 9 presents a typical output scan and analysis from the computer software controlling the differential scanning calorimeter. This particular graph is for a DSC scan of a glass transition Tg point for a nonirradiated virgin PEEK sample at room temperature, but the DSC scans for PEEK-GF samples are quite similar. Although the effects of the accumulated doses and the ambient temperature were investigated for the glass transition, crystallization, recrystallization, and melting temperatures with this method, only the effects for the glass transition temperatures are reported here since the other three temperatures are too high to be relevant for the scope of the present study. The crystallization, recrystallization, and melting temperatures were measured at 179 6 58C, 291 6 18C, and 335.7 6 0.48C, respectively. These temperatures are significantly higher than the maximum 1008C target decided upon in the design of the spent nuclear fuel disposal facility. The results from DSC reveal strong evidence of crosslinking in the PEEK-GF composite material ~Fig. 10!. For the composite material, the glass transition temperature slightly increased with increasing accumulated radiation dose, except for the composite material irradiated at 758C, which displays a slight drop of Tg with the maximum dose absorbed. The changes in the properties remained relatively modest ~,3.5%!. Figure 11 is that of a PEEK-GF composite material sample fracture area following a flexural test. Note that the magnification is 1017 for the top picture ~zero dose and pool temperature! and 482 for the bottom one ~1-MGy dose and 758C temperature!. It is apparent that the primary mode of failure is a fiber failure. While the samples having received the largest radiation doses displayed some actual signs of fiber pullout, this was not reflected in the mechanical strength and modulus of the composite material. Figure 12 presents the diffraction patterns for the PEEK-GF samples, focusing on the 18.9-deg peak, obtained via the wide-angle XRD method. This peak was chosen as it shows qualitatively the amount of crystallinity of the samples. Except for the composite sample at pool temperature, the peaks reveal in all other cases a decrease in crystallinity for the samples that have accumulated high radiation doses when compared to the nonirradiated samples. In composite samples at pool temperature, one observes an increase in crystallinity before the ultimate reduction. The influence of the temperature is made evident in these results as there is no initial increase of the crystallinity observed for the samples irradiated at 50 and 758C.
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Fig. 9. Typical DSC scan for Tg ~nonirradiated sample at pool temperature!.

VII. DISCUSSION The changes witnessed in the mechanical and thermal properties of the PEEK-GF composite material are attributed to two main factors in the experimental procedure: the radiation dose and the ambient temperature at the irradiation site. By keeping the factors constant, it was possible to see the effects that each of these factors had on the properties. As with all polymers, when PEEK is exposed to ionizing radiation, there are two types of reactions that occur simultaneously: chain scission and cross-linking. Depending ~among other effects! on the magnitude of the radiation dose absorbed, one of the two reactions is predominant and controls the nature of the property change. The graphite fibers are themselves very little affected by the radiation,11 but the interface between the fibers and the polymer matrix is sensitive, and the bonding can be altered by weakening or, in some cases, strengthening. For similar radiation doses, but in different temperature environments, the experimental work evidenced some slight variations in the physical properties of the samples. For example, the results of the elastic modulus show that after a low dose of radiation at pool temperature, minimal changes are observed. The largest variation of the flexural modulus observed was a 7.2% decrease of the modulus for the samples having received a low dose ~37 kGy! at 658C. A change in modulus is indicative of radiolytic effects.
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Fig. 10. Glass transition temperature for PEEK-GF composite material with respect to the duration of irradiation ~at half reactor power!, for the various temperatures investigated. 296

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VIII. RELEVANCE OF THE RADIATION DOSES IN THE SLOWPOKE-2 REACTOR POOL How can these results be put in the proper context of the actual sojourn of the polymer composite-based container filled with spent CANDU nuclear fuel bundles in the disposal site deep underground in the Canadian Shield? Previous research at the SLOWPOKE-2 Facility 25,26 at RMC has determined that the total dose rate at the irradiation site in the reactor pool is 37 kGy h 1. The same research also determined the relative contributions to the dose from the different particles as presented in Table III. An extensive investigation carried out at AECL ~Ref. 32! has produced tables of results for the inventories of the radioisotopes present in the CANDU fuel at various times such as at the fuel discharge from the reactor core, and a several times after, covering many centuries. The results presented in Ref. 32 are for a standard 37-element fuel bundle irradiated in a Bruce-A reactor under a thermal neutron flux of 1.26 10 14 n cm 2 s 1 during 228.72 days, thus having accumulated a burnup of 685 GJ kg 1 initial U ~7928 MW days tonne 1 initial U!. From the inventories in Ref. 32, the dose calculations could be carried out on the basis of the activities of the actinides for which the activities after a 10-yr decay period are larger than 3.7 10 5 Bq kg 1 ~10 5 Ci kg 1 !. As for the fission products, those included in the calculations had their activities after a 10-yr decay period .3.7 10 7 Bq kg 1 ~10 3 Ci kg 1 !. For the dose calculations, it was assumed that the filling materials in the container ~fuel bundle cladding, plus glass beads or thorium dioxide! could absorb the alpha and beta particles emitted by the radioactive isotopes in the fuel elements, as well as the recoil protons from the neutron collisions, and most of the neutrons. The only particles affecting the container walls were then the gamma photons and the energetic electrons created by the Compton, photoelectric, and pair production effects in close proximity of the container walls. The dose rates due to the gamma photons alone were computed by the Microshield TM software.33 The details of these calculations can be found in Ref. 34. Typical dose rates on the container walls have been determined as 19 Gy h 1 when no filling material is present in the container, 11 Gy h 1 when glass beads are used as the filling material in the container, and 0.05 Gy h 1 when ThO 2 is used as the filling material. Recall that these dose rates are for fuel having undergone a 10-yr decay period after discharge from the CANDU reactor core. Now, the contribution of the stripped energetic electrons resulting from the interactions of the gamma photons in the vicinity of the container wall can be accounted for using the results of an analysis done for the remote elevator position in the SLOWPOKE-2 reactor pool.35 At this position, the contributions of both fast and thermal neutrons and of the recoil protons ~and associated stripped electrons! are truly negligible. The
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Fig. 11. SEM micrograph of PEEK-GF composite material sample. Top: zero dose, pool temperature. Bottom: 1 MGy dose, 758C.

Most of the results for the yield stress were very small variations ~61%! around the value at room temperature for the not irradiated samples. The largest variation observed was a 5.8% decrease of the yield strength for the samples irradiated at 758C and having received a medium dose ~260 kGy!. This barely exceeds the value of 1s for the experimental results, which is equal to 5.4%. All these results lead to the conclusion the PEEK-GF composite material is very modestly affected after being irradiated at various temperatures from the flexural testing viewpoint. As evidenced by the DSC and XRD method analyses, the thermal properties and the crystallinity of the materials are affected by both radiation and elevated temperatures, albeit to a relatively modest degree, as described in Sec. IV. Finally, an examination of the SEM micrographs of the fractured areas of the PEEK-GF samples reveals that the primary mode of failure is a fiber failure, and for the samples having accumulated the largest radiation doses, there are some signs of fiber pullout, but not to the extent of affecting the results of the mechanical strength and modulus tests on the composite material.
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Fig. 12. Diffraction patterns for PEEK-GF composite material samples. Top: Pool temperature. Middle: 508C. Bottom: 758C.

results of this analysis indicate that the relative contribution of the energetic electrons produced by the Compton scattering, the photoelectric effect, and the pair production amounted to ;51% of the total dose rate. In the case of the container wall, the situation is quite comparable since the neutron and recoil proton contributions to the dose rate are also negligible. Therefore, the total dose rates in the container walls are essentially equal to the dose rates due to the gamma photons alone, divided by 51%. The total dose rates would then be 22 Gy h 1 and 0.1 Gy h 1 for the container filled with glass beads and thorium dioxide, respectively. The actual dose rate received by the PEEK-GF samples in this work was 37 kGy h 1,
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representing indeed an overkill when compared to the actual conditions to which the container walls are submitted in the deep disposal site. Yet, the composite material has behaved with only quite modest changes in its properties in such an aggressive environment. Another important consideration is the total accumulated dose over the 500 yr of exposure to the radiation produced by the spent fuel. In order to determine this dose, the dose rate is integrated over the time period, from a time zero defined as 10 yr after the withdrawal of the fuel from the reactor core and over a period of 500 yr afterward. The hourly dose rates given just above ~22 and 0.1 Gy h 1 ! correspond to yearly dose rates of 1.93 10 5
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Gy yr 1 and 877 Gy yr 1 for the container filled with glass beads and thorium dioxide, respectively. The integration over the years was carried out based on the data in Ref. 32 and using a numerical method. The cumulative doses to the container walls over the 500-yr period were then found as 12 MGy and 56 kGy for the glass beads and the thorium dioxide filling materials, respectively. If thorium dioxide is used as the filling material in the container, the cumulative dose over the 500-yr period is well below the dose imparted to the PEEK-GF samples in the SLOWPOKE-2 reactor pool irradiation site, and the results show clearly that the PEEK-GF properties would not be altered to compromise the composite materials integrity. Irradiations of PEEK-GF samples in the SLOWPOKE-2 reactor pool of ;324 h would have been needed to produce the 12-MGy dose determined for containers filled with glass beads. Such long irradiations could not be obtained with the equipment used for the research. If glass beads have to be used as the filling material, then it is not difficult to alter the design of the container by providing it with an internal layer of lead. For such a layer, a minimum thickness of ;4 cm would be sufficient to keep the cumulative dose below 1 MGy at the end of the 500-yr period. The knowledge gained with this research indicates that using thorium dioxide as the filling material not only would reduce significantly the cumulative dose to the container wall but also would contribute greatly to reducing the temperature of the container walls since the heat conduction coefficient of ThO 2 ~8.4 W m 1 K 1 ! ~Ref. 36! is much better than that of the glass beads ~0.78 to 1.09 W m 1 K 1 ! ~Ref. 37! for solid glass, and much less for glass bead filling material. In either scenario ~thorium dioxide or glass beads with a lead liner as filling material!, the maximum doses received by the PEEK-GF samples in this work are very representative of the actual doses imparted to the container walls in a real-life scenario. The extremely long half-life of 232 Th ~1.405 10 10 yr! results in an extremely small contribution of this radioisotope making the natural content of thorium to the dose rates imparted to the container walls. Another aspect of the validation of using the SLOWPOKE-2 nuclear reactor to simulate the radiation field to which the container walls would be submitted at the disposal site deep underground is related to the gamma spectrum. In a critical nuclear reactor at power, the gamma photon field is made of two contributions: that of the prompt gammas emitted by the fission process itself and that of the delayed gammas emitted by the fission products. The following equation 38 represents the gamma spectrum within the 1.0- to 7.0-MeV range: N~E ! 8.0e
1.10E

N~E !

26.8e

2.30E

MeV

and for energies above 7.0 MeV, the gamma population is low enough to be neglected. As for the delayed gammas, their total activity reaches a saturation point a few hours after the start-up of the reactor. The energy spectrum of these gammas may be given by the following equation: N~E ! 6.0e
1.10E

MeV

The total spectrum in the 1.0- to 7.0-MeV range is then given by N~E ! 14.0e
1.10E

MeV

Once the reactor is stopped, the gamma flux comes from the radioactive decay of the long-lived fission products. Their contributions have been studied by several groups of researchers 39 who presented their results with the spectrum subdivided into six or seven energy groups. These results show that at some 10 4 h ~417 days! after reactor shutdown, the populations of gammas within the energy groups have all decreased by four or five orders of magnitude and more, and the only significant contribution left at the end of that decay period was that of the group of photons with energies below 1.0 MeV. This trend is also valid for after 10 yr after removal of the fuel from the reactor. It can then be concluded that the irradiation of the PEEK-GF composite material in proximity of the core of the SLOWPOKE-2 nuclear reactor is achieved not only at a significantly higher dose rate but also with a much harder energy spectrum than the conditions under which the container walls would be subjected to at the disposal site deep underground. In the actual container case, the source of gammas is made of very long-lived radioisotopes producing lower dose rates and a softer energy spectrum, leading to less damaging effects per interaction of the photons with the composite material. While the SLOWPOKE-2 nuclear reactor does not quite produce a radiation field that represents very faithfully that of the disposal site, it does produce a much more aggressive and damaging radiation environment permitting one to assess the resistance of the polymer composite material in a definitely conservative manner.

IX. ERROR ANALYSIS The analysis of the results from mechanical testing methods shows very small standard deviations. The Instron instrument used for this work is of excellent quality and has excellent repeatability. Most of the error here comes from variations in the preparation of the samples. The small standard deviations are attributed mostly to the great care given to the sample preparation, and as Fig. 13 shows, the maximum standard deviations of the strength and modulus do not exceed 8%, with most values reported
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MeV

with a 615% error for the 1.0- to 4.5-MeV and 640% error for energies between 4.5 and 7.0 MeV. For energies below 1.0 MeV, the following equation 38 is more accurate:
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Fig. 13. Standard deviation of the mechanical properties.

being below 2.5%. The standard deviation was calculated for each set of samples ~six samples per set! using the usual equation 40 for the sample variance for sample sizes ,20: s2 1 n 1
n j 1

( ~ xj

x! 2 , S

where x j is the datum for the j th sample and xS is the average value for the n samples. The standard deviation is simply the positive square root of the sample variance. The SLOWPOKE-2 nuclear reactor at RMC is provided with an excellent automatic control system that maintains the neutron flux level ~hence the reactor power! to within 61% of the set point, and this for extended periods of time that can extend to several days of uninterrupted operation. This is the reason why some of the experimental data are reported as functions of irradiation duration since the error bars on these values are very small. The abscissae of the graphs have been provided with a second scale in terms of accumulated dose to help the reader with the interpretation of the results. However, problems are experienced when interpreting the irradiation durations in terms of radiation doses. Past research has been done at RMC to address this issue, and the dose
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rates were correlated to the reactor power levels and the thermal neutron flux by means of experimental data in conjunction with computer simulations of the nuclear reactor and surrounding pool.25,26 The uncertainty of the dose rate at the irradiation site used for this work was reported as 628%, which is a conservative figure as explained in detail in Refs. 25 and 26. This large uncertainty comes from three major sources: ~a! the difficulty in obtaining accurate experimental measurements of the flux of particles due to the high levels of these fluxes and the limitations of the detectors, ~b! the accuracy of the computer models used for the calculation of the particle fluxes, and ~c! the conversion of the values of the fluxes determined experimentally and computationally at the irradiation site into radiation dose rates through the energy transfer coefficients. There is also an uncertainty related to the actual time required to position and retrieve the samples at and from the irradiation site in the reactor pool. This last uncertainty is assessed at most to be on the order of only 3%. During the irradiations, the temperature of the chamber containing the samples was monitored and controlled through the combination of a thermocouple with digital readout and fully adjustable dc power supply. The thermocouple resided inside a dummy sample that was placed alongside the other samples within the irradiation chamber for accurate measurement of the temperature of the samples proper, not just the temperature of the ambient air. The thermocouple0readout system had an accuracy of 0.18C. The temperature was adjusted by means of an electrical current supply that could provide up to 20 A, although the current usually needed for this work did not exceed 10 A. The accuracy of the power supply readouts was 0.5 V and 0.5 A. At any one time, the temperature of the sample chamber never exceeded 638C of the set point for this work ~50, 65, and 758C!. The response of the thermocouple did not reveal any adverse effects on the equipment from the radiation. The irradiation chamber was not provided with measurement devices to assess the uniformity of the temperature within its volume. This was assessed as not necessary since the dimensions of the chamber were rather modest ~some 30 10 6 cm!; therefore, the temperature gradients in the chamber could be assumed as small. The Instron mechanical testing machine produced highly repeatable results due to the computer control and data acquisition system. Most of the error for these tests came from the fact that the strain was not measured directly from the samples but from recording the exact position of the crosshead, at every 0.3 s during the tests. Grip slippage and machine slack also could have altered the accuracy of the results, but in the present work, this was found to be insignificant causes of error. The DSC testing was carried out using an instrument that has an accepted error of 60.5%, thanks to the computer-controlled data acquisition system and thermal methods. This instrument is of superior quality, and the
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procedure included weighing the samples with an analytical balance with an accuracy of 1 mg. This error analysis confirms that the results obtained here are highly repeatable with very reasonable uncertainties. The major source of error thus comes from the interpretation of the exposure times in terms of accumulated radiation doses, and the second source of error in importance comes from the statistical spread of the results within each group of samples.

X. CONTAINER DESIGN CONSIDERATIONS At this point in the research, the dimensions of the proposed containers in the AECL study are retained for the calculation of the stresses and the thickness of the PEEK-GF composite material container walls. The container proposed by AECL has a 2.25-m height and a 0.620-m inner diameter and contains 72 standard CANDU 37-rod fuel bundles. If the titanium alloy making up the AECL container were to be replaced with PEEK-GF composite material, then the minimum thickness of the walls must be determined. At the repository site deep within a pluton in the Canadian Shield, it is estimated that the container must withstand a 13-MPa hydrostatic pressure, plus the weight of other containers stacked above it and the impact stress from the container being dropped during the transportation of the container to the disposal site and its placement within the vault. The purpose of this part of the research is at the present time to obtain a first assessment of the mechanical properties of the container made with the PEEK-GF composite material. In a subsequent phase of the research, actual mechanical testing is foreseen on models of the container in order to ascertain its mechanical behavior more accurately. In the calculations to determine the thickness of the container walls, the lowest values of strength and modulus determined experimentally are used, namely, a strength of 805 MPa ~dose of 259 kGy at 758C! and a modulus of 46.1 GPa ~dose of 37 kGy at 658C!. The container is first considered as a thin-walled right cylinder, i.e., for which the ratio of the interior diameter to the wall thickness must be .20. Since the interior diameter is 0.620 m, the wall thickness must be ,0.031 m. However, the thin-walled cylinder model assumes that the radial stress sr is zero. This is not assumed here, and the radial stress must be calculated with respect to the conditions presented above. It is also assumed that the tangential or hoop stress st and the axial stress sa are uniform throughout the wall thickness. The analysis must be conducted along the most probable mode of failure of the thin-walled cylindrical container, i.e., through buckling. The first buckling criterion considered here is caused by the tangential stress. This is explained by the so-called plastic hinge model. 41 Four nodes are identified as equidistant points along the circumference of the cylinNUCLEAR TECHNOLOGY VOL. 164 NOV. 2008

der. Under the tangential stress, the cylinder then collapses until two opposite nodes touch each other, the cross section of the cylinder changing from a perfect circle to two ellipse-shaped forms, with the long axes linking opposite nodes. In the plastic hinge model, a procedure is followed permitting the calculation of the pressure on the cylinders side to produce the work necessary to collapse the cylinder, this pressure being proportional to the yield stress and the square of the wall thickness, and inversely proportional to the square of the inside diameter of the cylinder. With all the forces and stresses accounted for through balance equations, it is possible to determine the minimum wall thickness for the container to resist to the net forces against the walls, these net forces being the difference between the external forces onto the container and the resistance forces offered by the materials within the container. For a 13-MPa external hydrostatic pressure, the results are reported in Table V. It is therefore seen that the minimum wall thickness is the value corresponding to the tangential buckling criterion. In the practical design of the container, some safety margins must be considered, and in this particular application, an outside pressure 25 to 50% larger than the pressure considered in these calculations should be used, yielding values from 49.7- to 54.4-mm wall thickness retained for the final design of the container. In a second step of this analysis, the maximum static load before buckling in the axial direction is determined. This is proportional to the elastic modulus multiplied by the second moment of area and inversely proportional to the square of the length of the cylinder. If the container is positioned vertically, this load is due to the hydrostatic pressure, unless other containers are stacked onto the container under study. In this latter case, every one of these containers would have a weight of 1774 or 1906 kg if glass beads or thorium dioxide is used as the filler material in the container. These values are determined from the assumption that a single container includes 72 CANDU spent-fuel bundles for a total of 1728 kg; a density of 2550 kg m 3 or 10 000 kg m 3 for the glass beads and the thorium dioxide, respectively; and a volume occupied by the filling material of 0.0178 m 3. If one

TABLE V Minimum Wall Thickness Required for a 13-MPa Hydrostatic Pressure Failure Criterion Tangential buckling Tangential stress Axial buckling Axial stress Minimum Wall Thickness ~mm! 44.5 5.01 3.05 2.40

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TABLE VI Total and Axial Stress Caused by Container Stacking, 13-MPa Hydrostatic Pressure Glass Beads Filler Number of Containers 0 1 2 3 Stacking Stress ~MPa! 0 0.187 0.374 0.561 Total Stress ~MPa! 13 13.2 13.4 13.6 Axial Stress ~MPa! 55.2 56.1 56.9 57.8 Stacking Stress ~MPa! 0 0.201 0.402 0.603 Thorium Dioxide Filler Total Stress ~MPa! 13 13.2 13.4 13.6 Axial Stress ~MPa! 55.2 56.1 56.9 57.8

considers that the bottom container has a thickness of 44.5 mm for its walls, the total area onto which the stress from the stacked containers is going to act can easily been computed as 0.0929 m 2. It is then possible to compute the total and axial stress on the bottom container for up to four stacked containers, and Table VI presents these values. It is then obvious that the safety margins mentioned above would be sufficient to cope with the container stacking issue. The possibility of dropping the container during its transportation to the repository site and its placement into the cavity in the underground disposal gallery must also be considered. The scenario considered in the present study is a vertical drop of 2 m such as inside the borehole carved in the floor of the underground gallery. In such a case, the maximum stress experienced in the container can be approximated by the static stress in the container multiplied by an impact factor n calculated by means of the following equation 42 : n 1 1 2 h D st ,

where D st is the static elastic strain, and h is the height of the container drop. For the PEEK-GF composite material, the impact factor is calculated as n 2.09 10 2. For this calculation, the container is considered outside the repository borehole ~i.e., without the radial stresses!, such that this impact factor acts as a stress concentration on the axial stress for a single container ~i.e., not stacked!. The axial stress on the dropped container from a 2-m height would then be equivalent to the axial stress at rest ~0.201 MPa for the container using the ThO 2 filler material! multiplied by the impact factor, resulting in a total stress of 42.0 MPa on impact. XI. CONCLUSIONS In this work, a polymer-based composite material made of PEEK and graphite fibers is proposed for the
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fabrication of a container that would be suitable for the ultimate disposal of CANDU reactor spent fuel bundles. The nuclear research reactor SLOWPOKE-2 at RMC was used to reproduce a mixed radiation field not only comparable to but also more damaging than the radiation field generated by the spent nuclear fuel on the containers walls. Samples made of a PEEK-GF composite material were irradiated in the pool of the reactor inside a temperature-controlled chamber and left to accumulate radiation doses up to nearly 1 MGy. At all the dose levels tested, the dominant effect observed was cross-linking, with some chain scission being a concurrent phenomenon caused by the radiations. However, the changes in the mechanical properties ~strength and modulus! that were observed were relatively minor and certainly not enough to cause any concern about the integrity of the PEEK-GF composite material. The radiation doses received by the samples in this study are significantly more than the radiation doses received by an actual container after 500 yr in the underground disposal site. Also, within the deep underground disposal site, the temperature of the containers walls would decrease relatively rapidly to values close to those of the ambient temperature of the plutonic granite rock, well below the 758C investigated here. The results obtained by the present study at this elevated temperature and high accumulated doses correspond to a scenario in which the container would remain at 758C for several centuries. This represents a very conservative assumption indeed. Yet, the results obtained demonstrate that the integrity of a container made of a PEEK-GF composite material would be ensured. Replacing the titanium alloy and the copper metal presently proposed with the PEEK-GF composite material investigated here thus represents a very promising option. The research considered using glass beads ~the option proposed by AECL! and also using sintered thorium dioxide as the filling material. The latter material would promote better heat transfer ~from its much higher density!. Most importantly, it would shield the container
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walls from the radiation emitted by the CANDU fuel bundles, thanks to the high-Z value ~90! for thorium. Finally, some aspects of the design of the containers were examined, such as determining the thickness of the containers walls assuring the integrity of the container. A thickness of ;50 mm would be a conservative value and is reasonable both in the context of the fabrication of the container and in keeping the costs at affordable levels.

research project. In addition, the financial assistance of the Natural Science and Engineering Research Council of Canada is gratefully acknowledged.

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XII. RECOMMENDATIONS In order to offset the uncertainties associated with the experimental data, this research can be extended by irradiating PEEK-GF composite material samples in order to accumulate higher radiation doses under higher temperatures, provided that the control problems encountered with maintaining temperatures .758C in the irradiation chamber could be solved. The present research is part of a larger research program in which the next step consists of irradiating the PEEK-GF samples in an even more aggressive environment in which the samples would be not only subjected to the mixed radiation fields at elevated temperatures but also in contact with acidic and alkaline solutions representing the groundwater at the disposal site deep underground. This would permit the determination of the chemical resistance of the polymer-based materials in addition to their mechanical and thermal resistance, again in a simulation of the containers dwelling time at the spent fuel disposal site over 500 yr and more. The mechanical behavior of the container fabricated with PEEK-GF composite material must be determined experimentally to validate the theoretical predictions achieved in this work. For this, scale models of the container have recently been fabricated with the PEEK-GF composite material to ascertain any problems related to the fabrication of actual containers with this material and to carry out mechanical testing to confirm the theoretical models used in this work. It is planned to continue the study to address the large reported error of the value of the dose produced by the SLOWPOKE-2 reactor at RMC, as a parallel project. Although this has actually a minor effect on the conclusions reached from this work, it would be appropriate to make use of improved computer codes now available to simulate the SLOWPOKE-2 nuclear reactor and of more accurate radiation measurement devices that have become available since the last study 25,26 was carried out.

ACKNOWLEDGMENTS
The authors wish to thank K. Nielsen and the staff of the SLOWPOKE-2 Facility at RMC and the technicians of the RMC Department of Chemistry and Chemical Engineering for their sustained and enthusiastic assistance with this demanding
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