Method of making microspheroidal nuclear fuels having closed porosity
United States Patent Googin et a1.  
 [ Apr. 29, 1975 METHOD OF MAKING MICROSPHEROIDAL NUCLEAR FUELS HAVING CLOSED POROSITY [75] Inventors: John M. Googin; Charles R.  
 Schmitt, both of Oak Ridge, Tenn.  
 [73] Assignee: The United States of America as represented by the United States Atomic Energy Commission, Washington, DC.  
 [22] Filed: Dec. 19, 1972 [21] Appl. No.: 316,625  
 Related US. Application Data [63] Continuation of Ser. No. 48,579, May 25. 1970,  
 abandoned.  
 [52] US. Cl 252/30l.1 R; 117/46 R; 264/.5;  
 [51] Int. Cl C09k 3/00 [58] Field of Search 423/7, 251, 252. 256, 260,  
 423/261; 252/301.1 S, 301.1 R; 264/.5; 1 17/46 R [56] References Cited UNITED STATES PATENTS 3,399,979 9/1968 Hamling 264/.5 X  
 3,403,008 9/1968 Hamling 423/256 X 3.434.809 3/1969 Swanson 423/7 X 3,438.749 4/1969 Lonadier et al. 264/.5 X 3,493,514 2/1970 Ashby et a1 252/30l.l 5 3,501,411 3/1970 Triggiani et a1. 252/301.l S 3,511,620 5/1970 Shimokawa et al.... 423/7 X 3.663.182 5/1972 Hamling 264/.5 X 3,673,101 6/1972 McKenney et al..... 423/256 X 3,764.550 10/1973 Block et a1 423/256 X Primary Examiner-Benjamin R. Padgett Assistant ExaminerE. A. Miller Attorney, Agent, or FirmDea.n E. Carlson; David S. Zachry; lrving Barrack [57] ABSTRACT 9 Claims, No Drawings METHOD OF MAKING MICROSPHEROIDAL NUCLEAR FUELS HAVING CLOSED POROSITY BACKGROUND OF THE INVENTION The invention described herein was made in the course of, or under, a contract with the US. Atomic Energy Commission.  
  This is a continuation of application Ser. No. 48,579, filed May 25, 1970 and now abandoned.  
  The present invention relates to a novel nuclear fuel composition characterized as microspheroidal particles consisting of a porous carbon matrix and an oxide or carbide of uranium uniformly dispersed within the volume of said matrix.  
  In the ideal sense, a model fabrication process for a nuclear fuel is one which is characterized by simplicity, economy of operation, and by its amenability&#39;to reproduce a nuclear fuel which meets product requirements for use in a power-producing reactor. In addition, it is most advantageous if the fuel is so constructed that it can readily be reprocessed for recovery of fissile and fertile values after its discharge from a going reactor.  
  It is accordingly the principal object of this invention to provide a nuclear fuel and a process for its fabrication which meets these aforementioned criteria.  
 SUMMARY OF THE INVENTION In its product aspect, this invention is concerned with a microspheroidal particle having a particle size in the range 5 to 2,000 microns. It consists essentially ofa porous carbon or graphite matrix containing a homogeneously dispersed phase consisting of an oxide, carbide, nitride, or silicide of a fissionable or fertile metal or alloy thereof. A unique feature of the porous matrix is that its porosity is mainly of the closed-pore type, of the order of 30 volume percent, as measured metallographically. A particular advantage of the microspheroidal particles of this invention is the fact that a considerable percentage of the fissionable or fertile values are found within the closed pores of the matrix which serve as a convenient trap for gaseous fission products generated during the course of the fission process. In instances where higher degrees of fission product required, are rquired, the spheroidal particle can be coated with pyrolytically deposited carbon or carbide layers to develop essentially complete gas impermeability. When a fuel loading of the microspheroidal particles of this invention has reached its useful life, it is readily removable from the reactor and can be processed by well known chemical reprocessing techniques to recover fissionable and fertile values as well as useful fission products. Such reprocessing in one suggested scheme would merely involve oxidation of the carbon or graphite matrix in air or oxygen at an elevated temperature sufficient to gasify the carbon, leaving a residue readily dissolvable in aqueous acidic media to produce a feed solution from which the dissolved fissionable and fertile values can be readily separated by well known solvent extraction techniques.  
  In its process aspect, the present invention is concerned with a process for the preparation of microspheroidal particles of the character described which comprises immersing or contacting spheroidal organic ion exchange resin particles or sorbing selected metal cations on an organic ion exchange resin to a desired loading, drying the loaded resin particles, and then carbonizing the dried resin. Among the ion exchange resins useful in making the porous microspheroidal particles of this invention are cation exchange resins containing sulfonic, phosphonic, or carboxylic acid as the functional group at sites along a polymeric backbone chain and anion exchange resins containing quaternary ammonium, primary, secondary, and tertiary amine groups along a backbone polymer chain. Sorption on anion exchange resins occurs from acidic solutions such as aqueous solutions of nitric, sulfuric, or carbonic acid. 7  
  Among the particular commercial ion exchange resins useful in the processof this invention are Dowex 1, Dowex 21K, Dowex 50x12, and Dowex 50W, although ion exchange resins from other commercial vendors would be equally satisfactory. Dowex 1 and Dowex 21 K are anion exchange resins incorporating a quaternary ammonium type of structure in which the four substituents on the nitrogen atom are a polymeric benzyl and three methyl groups.  
 &#39; Dowex 50W is a strongly acidic cation resin made by the nuclear sulfonation of styrene-divinylbenzene beads. It may be designated chemically as R&#39;SO H, where R represents the polystyrene resin.  
  The degree of crosslinkage in an ion exchange resin bead refers to the fraction of divinylbenzene it contains. For the Dow Chemical Company resins, the per cent crosslinkage is indicated by a number following an X after the name of a particular resin. Thus, Dowex 1X1 resin is made from a copolymer containing&#39;l per cent divinylbenzene and Dowex 1X10 resin would contain 10 per cent divinylbenzenel The divinylbenzene content contributes the third dimension to the polymer network and makes it insoluble. The very low crosslinked resins are highly swollen, allow faster diffusion of ions within the resins, and are soft and easily deformed. The higher crosslinked 10 percent) resins are harder and do not swell as much when exposed to solutions.  
  The conditions under which a desired degree of metal cation loading can be obtained in a reproducible manner are well known in the available literature. See, for example, Anion Exchange of Uranium in Nitrate Solutions, Journal of Chemical and Engineering Data, Vol. VI, No. 2, April 1961, p. 217, etc.  
  After loading has been accomplished to the extent desired, the loaded resin particles are then separated from the solution either by decantation or filtration. Excess liquid is removed by washing and the separated resin particles are then dried to remove excess moisture. The loaded resin particles should be thoroughly dried at non-carbonizing temperatures. If they are not, there is a risk that subsequent carbonization will cause cracking or decrepitation of the particles as the resin is converted to&#39;carbon or graphite. Drying to remove moisture can be effected at a temperature of about 1 10C.  
  The dried, metal-loaded ion exchange resin spheres are then subjected to a carbonization reaction by heating slowly in an inert atmosphere to a temperature adequate to convert the resin spheres to carbon using a controlled heating cycle. Normally, a temperature of 900l C. is adequate to accomplish carbonization. A satisfactory heating rate is one which allows gases from the internal volume of the metal-loaded resins to be dispelled without excessive internal particle deformation, decrepitation, or cracking of the particles. In order to maintain the sphericity of the particles, it is preferred that the particles be carbonized in a fluidized bed using an inert gas as the fluidizing medium.  
  In describing this process for making microspheroidal particles it should be made clear that the sphericity desired in the final product is a function of the degree of sphericity of the unloaded resin beads, and the subsequent processing involved in converting the metalloaded beads to carbon or graphite. These and other specific aspects of the invention discussed heretofore in general terms will be made clearer in the specific embodiments to be described in the following examples.  
 EXAMPLE I A batch of Dowex lXl (50-l00 mesh) anion exchange resin was converted to the nitrate form by treatment with 0.9M NH NO 0.1M HNO solution in an ion exchange column until the column effluent was free of chloride ion. The resin was then rinsed with distilled water. Three l-gram portions of the resin were loaded with uranyl nitrate by equilibrating with 800 ml of 6.0M NH NO solution containing sufficient dissolved uranyl nitrate to provide various uranium loadings of 50 to 150 g U/Kg dry resin according to predetermined equilibrium relationships. The resins were then filtered, air dried, dried in an oven at 100C, and carbonized under flowing helium. One l00-gram portion was carbonized at 500C., another at 700C, and a third at 850C. Each portion was carbonized for 1 hour. The analytical results of these three portions are shown in Table 1.  
 TABLE I was noted as comparable to that which took place during carbonization.  
  Photomicrographs of cross sections of the carbonized uranium-loaded beads after 950 and 2,200C. heat treatments showed the carbonized beads to contain internal porosity or fissures. Cross sections of Dowex 21K resin beads before and after uranyl nitrate adsorption have been examined to show that the internal voids and fissures are not inherent in the anion exchange resin structure before carbonization.  
  X-ray diffraction studies of the uranium-loaded resin after carbonizing at 950C. and high firing at 1,400&#34;, l,700, and 2,200C. under flowing helium were made in order to identify the chemical form of the uranium associated with the carbon matrix at these various firing temperatures. A comparison of the X-ray diffraction patterns obtained with U0 UC, graphite, and U 0 standards showed that at 1,400C. the uranium is present as almost all U0 At 1,700C., the diffraction pattern of the coked resin shows the presence of U0 and UC, with some carbon. A comparison of the X-ray diffraction patterns of the resin high fired at 2,200C. with standard patterns of uranium monocarbide and uranium dicarbide showed the presence of both UC and UC A summary of the uranium content, carbon content, and mercury displacement density for uranium-loaded Dowex 21 K resin beads after heating under flowing helium at 950C., 1,700C., and 2,200C. is given in Table I1.  
 carbonization of Uranium-Loaded lon Exchange Resin initial Carbonization Sample Uranium Temperature Coke Analysis Nitrogen No. Loading&#34; (C. Color gU/g Carbon ppm lEC-1 56.5 500 Brown 0.224 55.16 360 lEC-Z 92.1 700 Black 0.3582 47.48 243 [EC-3 135 .6 850 Black 0.4486 38.79 189 &#34;Gram uranium per Kg dry resin. &#34;LU-hour soak time in flowing helium.  
  Spectrographic analyses of pulverized coke product mesh) indicate that a high degree of uranium and carbon purity is attained by this method.  
  The foregoing example is included to show that variable loadings of uranium can be attained, that some decomposition of the resin occurs at temperatures below 950C., but that complete conversion of the resin to carbon requires higher carbonization temperatures.  
 EXAMPLE 11 slower heating cycle is desirable to avoid large internal fissures that may resultfrom dispellation of volatiles at too rapid a rate. The batch of 950C.-carbonized lresin beads was then heated in flowing helium for three hours at at least 1,700C. and not more than 2,200C. in a carbon induction furnace. No significant shrinkage TABLE 11 Properties of Coked, Uranium-Loaded Ion Exchange Resin Heat Treatment Density C. g U/g Coke Carbon g/l These data indicate that crystallization is rather incomplete at 950C. as shown by the large increase in X-ray line intensities upon high firing at 2,200C.  
  Cross-sectional examination at 1,000 magnification of elongated and spherical beads after high firing at 2,200C. showed the uranium carbide homogeneously dispersed in the solid portion of the carbonized bead as pepper-like grains.  
 EXAMPLE 111 One pound of Dowex 50W cation exchange resin microspheres, having 50-100 mesh size, was soaked for 16 hours in a uranyl nitrate solution. This solution was prepared bydissolving U 0 in 8N nitric acid. Subsequent dilution with distilled water produced an approximate 0.5&#39;N U0 (N0 solution.  
  The loaded resin microspheres were dried at 110C. for 16 hours after which they were carbonized in a fluidized bed using helium as the fluidizing medium. Carbonization was accomplished at 1,000C. using a maximum temperature rise of 200C/hr.  
  The resultant uranium-loaded microspheres contained about 22 per cent uranium by weight in the form of USO, as indicated by X-ray diffraction analysis. (The sulfur was present because sulfonated cation exchange resins were used. At 1,600C., uranyl nitrate on sulfonated cation resins converts to UO UC as indicated by X-ray diffraction analysis. Compounds of uranium and oxygen would result if the carboxylic acid form of cation exchange resin were used.) They had a density of about 1.9 g/cc and an open porosity of about 40 percent. The microsphere products were further characterized by metallography and microradiography. These techniques showed that a uniform distribution of uranium in the microsphere was achieved.  
  uranium-containing microspheres prepared as described in Example 111 were coated with pyrolytic carbon to give either an interrupted duplex coating or a monolayer coating. For the interrupted duplex coating, a 20-micron-thick, low-density coating (about 1.6 g/cc) was applied using propylene in a fluidized bed at l,250C. This was followed by the application of a 50- micron-thick, high-density layer (about 1.8 g/cc) also using propylene but increasing the temperature to 1,900C.  
  Monolayers of both 60-micron and 80-micron thickness were applied to some of the microspheres in a fluidized bed using propylene at 1,400C. These coatings had a density of about 1.75 g/cc.  
 EXAMPLE IV A batch of Dowex 5OX12 cation exchange resin (100-200 mesh spheres) in the hydrogen form was contacted with uranyl sulfate solution (approximately 200 gU/liter) for 48 hours using magnetic stirring. The resin was filtered, rinsed rapidly with distilled water to remove any residual mother liquor, and dried at 1 C. This treatment provided a resin uranium loading of 7.32 grams uranium per kilogram of dry resin. After carbonizing with helium at 900C, the resin spheres analyzed 1.85 per cent uranium, 79.18 per cent carbon, and 6.08 per cent sulfur. By subsequent high firing to temperatures of 1,800C. or higher in an inert atmosphere, the sulfur can be essentially completely removed.  
  ln the examples, the process of forming uraniumcontaining microspheroidal particles is provided as a specific embodiment. It should be understood, however, that the general technique described in forming uranium-containing microspheres can be adapted for making actinide oxideor carbide-containing microspheres of plutonium and thorium or mixtures of uranium, thorium, and plutonium. In addition, it should be noted that alloys of the actinides can also be formed as inclusions within the internal volume of the carbonized or graphitized matrix by appropriate loading of the resin. For example, where it is desired to form a microsphere containing a uranium-zirconium alloy, the resin is loaded with uranium and zirconium salts in the proportions corresponding to the desired alloy composition and then the process of microsphere formation proceeds by the appropriate carbonization or graphitization reactions.  
 What is claimed is:  
  l. A process for forming a nuclear fuel which comprises contacting ion exchange resin beads with an aqueous solution of an inorganic salt of at least one actinide metal, separating the actinide-loaded resin beads from the solution, drying the separated beads, and then carbonizing the dried beads at a temperature in the range l,400-2,200C. to form spheroidal particles with closed porosity containing the actinide metal as an oxide or carbide dispersed within a continuous carbon matrix.  
  2. The process according to claim 1 in which the dried beads are heated to a temperature in the range 1,4001,700C. and the thus formed spheroidal particles contain U0 dispersed within a continuous carbon matrix.  
  3. The process according to claim 1 in which the dried beads are heated to 1,700C. and the thus formed spheroidal particles contain essentially U0 and UC dispersed within a continuous carbon matrix.  
  4. The process according to claim 1 in which the dried beads are heated to 2,200C. and the thus formed spheroidal particles contain essentially UC and UC dispersed within a continuous carbon matrix.  
  5. A process for forming a nuclear fuel which comprises contacting ion exchange resin beads with an aqueous solution of a uranyl salt for a period of time to effect exchange of uranyl ions with the ion exchangeable sites on the resin, separating the uranium-loaded resin beads from the solution, drying the separated beads. and then heating the dried uranium-loaded resin in a non-oxidizing atmosphere to a temperature in the range 1,4002,200C. to produce spheroidal particles with closed porosity, said particles containing U0 UC. or UC as a dispersed phase within a continuous carbon matrix.  
  6. The process according to claim 5 in which the ion exchange resin beads are cation exchange resins containing sulfonic, phosphonic, or carboxylic acid groups as ion exchangeable sites.  
  7. The process according to claim 5 in which the ion exchange beads are anion exchange resins containing primary, secondary, tertiary, and quaternary amine groups as ion exchangeable sites.  
  8. A process for forming a. spheroidal uranium fuel particle which comprises contacting a sulfonated cation exchange resin resulting from the copolymerization of styrene and divinylbenzene: with an aqueous solution of a uranyl salt for a period of time sufficient to effect ion exchange of uranyl ions with ion exchangeable sites in the resin, separating the uranium-loaded resin from the solution, drying the separated beads, and thereafter heating the dried resin heads at a rate not exceeding 200C. per hour to a temperature of about 1,000C. to produce a porous spheroidal matrix of carbon containing a compound of uranium, oxygen, and sulfur as a dispersed phase.  
  9. A process for forming a nuclear fuel which comprises contacting ion exchange resin beads with an aqueous solution of an inorganic salt of at least one actinide metal, separating the actinide-loaded resin beads from the solution, drying the separated beads, carbonizing the dried beads at a temperature in the range l,4002,200C. to form spheroidal particles with closed porosity containing the actinide metal as an oxide or carbide dispersed within a carbon matrix, and then applying at least one pyrolytic coating on the surface of each of said particles.