Improvement in Retention of Solid Fission Products in HTGR Fuel Particles by Ceramic Kernel Additives
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FORMAL REPORT GERHTR-159 UNITED STATES-GERMAN HIGH TEMPERATURE REACTOR RESEARCH EXCHANGE PROGRAM Original report number ______________________ Title Improvement in Retention of Solid Fission Products in HTGR Fuel Particles by Ceramic Kernel Additives Authorial R. Forthmann, E. Groos and H. Grobmeier Originating Installation Kemforschtmgsanlage Juelich, West Germany. Date of original report issuance August 1975_______ Reporting period covered _ _____________________________ In the original English This report, translated wholly or in part from the original language, has been reproduced directly from copy pre pared by the United States Mission to the European Atomic Energy Community THIS REPORT MAY BE GIVEN UNLIMITED DISTRIBUTION ERDA Technical Information Center, Oak Ridge, Tennessee DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document. GERHTR-159 Distribution Category UC-77 CONTENTS page 1. INTRODUCTION 2 2. FUNDAMENTAL STUDIES 3 3. IRRADIATION EXPERIMENT FRJ2-P17 5 3.1 Results of the Fission Product 8 Release Measurements Improvement in Retention of Solid 3.2 Electron Microprobe Investigations Fission Products in HTGR Fuel Particles 8 by Ceramic Kernel Additives. 4. IRRADIATION EXPERIMENT FRJ2-P18 16 4.1 Release of Solid Fission Products 19 4.2 Electron Microprobe Studies 24 by R. Forthmann, E. Groos, H. GrObmeier 5. SUMMARY AND CONCLUSIONS 27 6. ACKNOWLEDGEMENT 28 7. REFERENCES 29 2 - X. INTRODUCTION Kernforschungs- anlage JUTich JOL - 1226 August 1975 Considerations of the core design of advanced High-Temperature Gas-cooled GmbH IRW Reactors (HTGRs) led to increased demands concerning solid fission product retention in the fuel elements. This would be desirable not only for HTGR power plants with a helium-turbine in the primary circuit (HHT project), but also for the application of HTGRs as a source of nuclear process heat. Improved solid fission product retention of pyrocarbon-coated fuel particles can be obtained by two different methods: Improvement in R etention of Solid (a) Deposition of carbide interlayers (e.g. silicon carbide or zirconium carbide) as an additional diffusion barrier in the pyrocarbon coating, Fission Products in HTGR Fuel Particles by Ceramic K ernel Additives (b) Improvement of the kernel retention by chemical reaction of the fission products with suitable kernel additives forming stable fission product by compounds. R. Forthmann E. Groos H. Griibmeier ABSTRACT Increased requirements concerning the retention of long-lived solid fission products in fuel elements for use in advanced High Tempera Silicon carbide interlayer Ceramic kernel additives ture Gas-cooled Reactors led to the development of coated particles with improved fission product retention of the kernel, which re present an alternative to silicon carbide-coated fuel particles. Two irradiation experiments have shown that the release of strontium, Fig. 1: METHODS OF IMPROVED FISSION PRODUCT RETENTION IN COATED FUEL barium, and caesium from pyrocarbon-coated particles can be reduced by orders of magnitude if the oxide kernel contains alumina-silica PARTICLES AT HIGH TEMPERATURES additives. It was detected by electron microprobe analysis that the improved retention of the mentioned fission products in the fuel kernel is caused by formation of the stable aluminosilicates The principle of the two methods is shown in figure 1. At the left side of SrAlgSijOg, BaAlgSi^Og and CsAlSi^Og in the additional alumina- the figure the kernel releases solid fission products (marked by arrows) silica phase of the kernel. which easily penetrate the porous and dense inner pyrocarbon layer (PyC = pyrocarbon), until they are retained by the silicon carbide layer (SiC = silicon carbide). This method is well known and has been investigated at 1 many laboratories. At the right side of the figure the coated particle contains ceramic kernel additives (e.g. AljOg + SiC>2), the solid fission products are does not form solid solutions with U02 and is found in the ceramic inclusions retained in this second ceramic phase of the kernel by solid state chemical together with zirconium and uranium forming BaZrOg and probably BaUG^. Most reactions. In this case an additional silicon carbide layer is not necessary. of the caesium is present as metal vapor, only small amounts form the rather volatile compounds CsJ and CSgMoO^. Since Sr and Ba form zirconates in kernels without additives, an excess of Zr02 in the fuel kernel cannot be expected 2. FUNDAMENTAL STUDIES to be very effective for retaining these fission products. The BaO vapor pressure of BaAlo0. was found to be about one order of magnitude lower than Out-of-pile investigations on coated particles containing artificial solid that of BaZrO^ . Therefore an improvement of the Ba retention and possibly fission products, which had been introduced during the kernel fabrication of the Sr retention by A1203 additives can be expected. The best out-of-pile process, gave preliminary information on the fission product retention results, however, were obtained by using a combination of A1203 and Si02 efficiency of ceramic kernel additives. Table I shows some of these kernel additives. These additives are insoluble in U02 as well as in Th02 additives and their possible fission product compounds. and appear as a second phase in the fuel kernel. In this second ceramic phase not only Sr and Ba can be retained by formation of very stable THERMAL NEUTRON aluminosilicates of the feldspar type, but also Os by forming stable alumino CROSS SECTION MELTING POINT ADDITIVE FISSION PRODUCT COMPOUND silicates as CsAlSiO., or CsAlSio0c. OF THE METAL ( °C ) 4 2b (barns) An important question is the compatibility of these additives with the pyro carbon coating of the fuel particles. During the ijrradiation oxide fuel kernels Zr02 0.188 SrZrOg 2800 produce an increasing carbon monoxide pressure with increasing heavy BaZrOg metal burn-up which may reach values up to 100 bars in the coated particle. SrNb_0c If the equilibrium carbon monoxide pressures of the additives Zr02, A^Q^, 2 o Nb.Os 1.15 BaNb_0c 1455 Si02 in contact with carbon are plotted as a function of temperature CsNb2,6°7 1416 (Fig. 2), it can be seen that these CO pressures are below the observed CO pressures in irradiated coated particles. The same is valid for the fission A12°3 0.235 SrAl204 1790 5) product compounds as far as thermodynamic data are available. It can be BaAl204 1815 concluded that the additives and their fission product compounds will be thermodynamically stable in coated particles at HTGR operating conditions. A12°3 0.235 SrA12Si2°8 - 1 These thermodynamic considerations were confirmed out-of-pile,using coated + sio2 0.16 BaAl2Si208 S. >1700 particles with kernel additives and artificial solid fission products by CsAlSi-0c 2 b heat treatmant in the temperature range of 1000 - 1800°C. 2 CsAlSi04 Table I: KERNEL ADDITIVES AND FISSION PRODUCT COMPOUNDS The chemical state of solid fission products in irradiated U0o kernels is 3) ^ known from electron microprobe analysis : Strontium is oxydized to SrO and forms partially solid solutions in the U02 phase, the other part is concentrated in zirconia containing ceramic inclusions forming SrZrO^. Barium - 5 - 6 1200 K Irradiated particles 1000 1100 1200 1300 1400 Temperature (®CI Fig. 2: CARBON MONOXIDE PARTIAL PRESSURES 3. IRRADIATION EXPERIMENT FRJ2-P17 In the FRJ2-17 experimentspyrocarbon-coated fuel particles with fission product retaining kernel additives were irradiated for the first time. The e \ kernels were prepared by using the H-process» the starting solution of £tJ02(1 ^N03^2 g U/l) was mixed with calculated amounts of ZrO(NOg>2, A1(N03>3 and SiO^ powder (grain size < 50 ^um) respectively. After sintering,the additives were present in the form of oxides in the UO^ kernel matrix. The kernels were coated with two pyrocarbon layers (BIS0- coating): a porous layer (density = 1.0 g cm by pyrolysis of acetylene and a dense layer (density = 2.0 g cm ) by pyrolysis of propene. The coated particles were embedded in a graphite matrix (Fig. 3) and the fuel compacts were irradiated at temperatures ranging from 1100 to 1200°C. The main data of three particle varieties of this experiment are given in table II. Fig. 3: MICROGRAPH OF A FUEL COMPACT SECTION (FRJ2-P17) 3.1 Results_of_the_Fission__Product_Release_Measurements KERNEL 1 2 3 Fractional release values are available only for fission products remaining in material U°2 U02/Zr02 U02/Al,03/Si02 the graphite matrix of the compacts. The values of Zr, Sr and Ba are composition summarized in table III for three different kernel compositions. The fractional (wt. %) 95 release of Zr is comparable with the fraction of free uranium on the U02 100 89,7 95,1 _7 , particle surface (below 5.10 ) and is apparently caused by fission of this Zr02 - 10,3 - free uranium. As expected, zirconia additives do not retain Sr 90, but A12°3 - - 2,2 alumina-silica additives reduce the Sr 90 release by two orders of magnitude, sio2 - - 2,7 and the Ba 140 release by three orders of magnitude. This retention efficiency enrichment is comparable with the retention properties of silicon carbide coated particles. (% 235y) 15 15 15 diameter (^um) 684 682 671 The fission products Cs 134, Cs 137 and Ag 110m did not remain in the graphite matrix of the fuel compacts. About 70 - 85 % of the caesium was released from COATING the compacts and was found on the inner graphite spine, on the outer graphite tube, and on the steel wall of the capsule. It must be assumed that this material PyC PyC PyC released caesium contaminated the fuel compacts with lower caesium release. total thickness (^um) 180 199 178 As compacts with different kernel varieties had been irradiated in one capsule, it was not possible to obtain definite fractional release data for IRRADIATION caesium. From measurements of the activity of Ag 110m very high fractional release values resulted (between 4.4 .