DRAFT

CURIUM-244 HEAT SOURCE FABRICATION*

Contribution to AVAILABILITY AND COSTS OF CURIUM-244 FROM POWER REACTOR FUEL WASTES

Eugene Lamb, ORNL D. G. Albertson and Paul Brown General Electric

To be presented at Intersociety Energy Conversion Conference Philadelphia, Pennsylvania

August 1973
NOTICE
This report was prepared as an account of work sponsored by the United States Government. Neither the United States nor the United States Atomic Energy Commission, nor any of their employees, nor any of their contractors, subcontractors, or their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness or usefulness of any information, apparatus, product or process disclosed, or represents that its use would not infringe privately owned rights.

MASTER

*Research sponsored by the U. S. Atomic Energy Commission under contract with Union Carbide Corporation.
DISTRIBUTION OF THIS DOCUMENT IS UNLIMITED

DRAFT ELtskw May 23, 1973

Curium-244 Heat Source Fabrication Curium Fuel Form Fabrication The selection of curium sesquioxide (2'-'tCm203) as the fuel form for isotopic power applications was on the basis of its thermal stability, high melting point (2265C), low vapor pressure, compatibility with potential encapsulant alloys, and fabricability. Its relatively low thermal conductivity (0.01698 W/cm.C at 1000C) can impose a limitation on the diameter of fabricated ^^Cn^Oa fuel forms in order to maintain the centerline temperature in a safe operating range. Because of its inherent neutron emissions, fabrication operations involving hundreds of grams of ^'Cn^Os must be conducted remotely in shielded cells with manipulation of equipment and materials by master-slave manipulators. For applications in thermoelectric generators the external temperature of the zt*kCm203 fuel will be in the range of 800-l400C, and the diameter of the fuel will be in the range cf 0.25 to 1.0 in., depending on the design of the converter system. Fabrication of densifled
2tft

*Cm203

fuel pellets in this size range has been demonstrated using the hotpress method. A prototype source was assembled and operated for 22 months using 412 g of
2tfJf

Cm203 emitting 956 t . The fuel consisted of 14 hot-

pressed pellets, 0.531-in. diameter by 0.63- to 0.9-in. high. Developmental quantities of

2tfl

*Cm have been furnished by Savannah

River Laboratory for determination of properties and development of fabrication techniques at ORNL. For the large-scale applications envisioned in the late 1970's, the large quantities of relatively low-cost
2<ft

*Cm

required will be supplied by recovery from power reactor fuel reprocessing wastes. The isotopic composition of curium in fuel 150 days after

discharge fr^.s a Pressurized Hater Reactor (PWR) after 33,000 KHD/Tonne exposure is given in Table 1.

/ i Y'.

Table 1. Isotopic Composition of Curium in PWR Fuel 150 Days After Discharge With 33,000 KWD/T Exposure Isotopic Haas 242 243 Weight () % 13.67 0.20 80.3 5.26 0.6 Half-Life (years) 0.446 32. 18.12 3265. 4655. Heat Generation per Gran of Curium <w ) r 16.21

244
245 246

2.28

Because of the relatively high concentrations of 2<>2Cm in the power reactor fuel at discharge, the heat generation rate of the isotope is a factor of 7.1 higher than that of 2t>t>Cm per gran of curium. meet the apecification that the heat contribution from
2t|2

In ordtr to

Ca b no wore

than IX of the heat generated by 2****C at tine of generator fueling, a decay period of five years will be allowed from reactor discharge tc generator fueling. The iaotopic composition of the curium at five years after reactor discharge is given in Table 2.

'V \

Table 2. Isotopic Composition of Curium

') / '/j

Recovered From PWR Waste (33,000 MWD/T) Five Yeara After Reactor Discharge Isotopic Mass 242 243 244 245 246 Weight Z 0.015 0.249 91.75 7.16 0.82

This necessary decay period coincides nicely with the planned storage of aqueous fuel reprocessing wastes for three to five years before calcining at some facilities. The recovery of curium would be planned to occur at about four years after reactor discharge, at which time the troublesome short-lived heat products oong the fission products as well m* the 2<*2C will have decayed to reasonable values for ion-exchange and solvent extraction operations. Based on previous processing of
2<t<>

Ca at Savannah River Laboratory,

the separated product will be precipitated as curium oxalate which will be calcined to prepare slightly substoichiometric CmO 2 as the fora to be shipped to the fuel fabrication plant. In the case of fuel prepared as hot-pressed pellets, the following steps are involved in the fuel fabrication process:

1. Remove CmOz from shipping can*, assay heat content, impurities, and melting point. 2. Convert to CS2O3 by heating at 1000*C in vacuum or inert atmosphere for 4 hr. 3. Load hot-press die (graphite) with assayed increment in argon atmosphere. 4. Vacuum hot-press at 1450*C and 4000 psi for 1 hr. 5. Eject pellets in argon atmosphere, measure, and weigh. ' 6. Oxidise residual carbon on pellet surface by heating at 1000*C for 4 hr in argon with an oxygen concentration of ^2000 ppm; reduce oxygen concentration to <100 ppm and cool to cell temperature. 7. Load and weld inner capsule (post-impact containment shell), quality control procedures. 8. Load and weld heat source assembly, quality control procedures.

The design of a vacuum hot press used in the ORNL fuel development program is shown in Pig. 1 and typical hot-pressed pellets are shown in Fig. 2. The resulting
2t|t

*Cm2C>3 pellets will have a maximum density of 10.3

g/cm3, or 90% of theoretical density with allowance for the effect on density of 3% chemical contaminants consisting cf light elements. The specific power and power density of hot-pressed Table 3. Table 3. Specific Power and Power Density of 2 +1*Cm203 Recovered From PWR Waste Time After Reactor Discharge (years) 4 5 6 8 9 10 Specific Power* (W/g of Cm 2 O 3 ) Power Density (W/cm3 of
2l>l

*Cm203 are given : n l

2.30 2.21 2.13 2.05 1.98 1.90 1.83

23.68 22.80 21.96 21.15 20.36 19.61 18.88

*Heat contribution from 2**2Cm is not included. The contribution of 2t*2Cm at five years is 0.02 W/g of C1B2O3. Power density calculated on the basis of 10.3 g/cm3 fuel density.

Fig. 1. Vacuum Hot Press. Fig. 2. Typical Hot-Pressed Pellets.

Fuel forms of ^^Cn^Oa other than hot-pressed pellets may be feasible for future applications. Other forms under consideration are as-prepared C1112O3 powder and sintered C1112O3 shards (prepared by crushing sintered Cm203 and sizing of particles) which are tamped or step-pressed into a capsule. The use of C1112O3 powder loaded directly into a capsule offers a potential saving of 50% of the fabrication cost of hot-pressed pellets if a converter system can utilize fuel which is in the order of 50% of theoretical density. Experience in the fabrication of this fuel form is not available at this tine. Curium Fuel Handling Procedures The handling of curium fuel after It is converted to C1112O3 requires that careful attention be given to the quality of the cell atmosphere and heat removal from the powder. Because CU2O3 can be oxidized to higher oxides of curium in an oxygen atmosphere below 8G0*C, a dry, inert atmosphere (urually argon) with <100 ppm 0 2 must be maintained. A high quality inert atmosphere is attained in existing cells by installing sealed plastic boots on the master-slave manipulators and good seals on all access doors and pass-throughs. In a future production-scale source fabrication plant commercially available manipulators with internal seals can be used. The present practice is to maintain 0.1 to 0.3 in. W.6. vacuum in the cell with a low purge rate of argon without recycle. The heat from the curium fuel is removed by chilled water recirculating through a heat exchanger plate constituting the entire floor of the cell. In addition, careful attention to the thickness of layers of C1U2O3 and to total quantity in a single batch must be given because of self-sintering and formation of clumps

due to internal heating. In general, batch quantities of powder.are less than 10 g and layers of powder are less than 1/4-in. thick to prevent clumping. Vessels and tools used fo/ in-cell transfers of curium oxide powder and pellets are stainless steel and are individually cooled where necessary to provide for heat removal from larger quantities of curium. Containers for long-term storage are platinum-lined to preclude possible contamination of the curium fuel. Curium Fuel Encapsulation A number of metals and alloys are being considered as potential encapsulants for ^'Cn^C^ for space applications. These include superalloys (Haynes-188, Hastelloy C-276), refractory alloys (W-26% Re, T-lll), and noble metals and alloys (Ir, Ft20% Rh). Welding procedures are developed for a particular alloy and source design using available remote velding technology developed at ORNL for the inert gas-tungsten arc. plasma arc, or electron beam methods. Quality control procedures used on completed welds include helium or
85

Kr leak testing and sectioning

of samples welded under the same conditions and immediate in-timing to the fueled capsule weld. Remote ultrasonic probe determinations of weld quality and penetration has been utilized for
90

Sr heat sources and can be

adapted to curium sources having the necessary weldment design for this procedure. Careful consideration of clearance between pellets and the capsule wall must be given for a feasible and economical laodlng operation. This clearance is usually a compromise between the desire of the fuel fabricator to have plenty of clearance to preclude any binding of pellets and the

need the system designer to minimize gap width and temperature increase across the gap. In general, a diametral clearance of 0.020 in. for capsules several inches in length is workable. A fabrication loading tolerance of 5% of the nominal thermal power is allowed for single pellets or for small units contining less than 10 pellets. This tolerance represents the estimate of ability to achieve the nominal power and does not represent the variation in the absolute measurement. In the case of assembly of multiple units or pellets, lower power units can be matched against higher power units so that the overall loading tolerance for assemblies using 10 or more small units or pellets will be 2%. Decontamination of singly encapsulated heat sources to the usual low surface contamination specifications required prior to assembly into a power generator usually represents a considerable expenditure of time and money. If the system design permits, a second encapsulation in a clean cell separate from the fuel loading cell greatly reduces the surface contamination problem. Production-Scale Curium Source Fabrication Plant Study A preliminary study has been made for the conversion of an existing manipulator cell facility to provide a nominal curium source fabrication capability of 10 kg of
2tft

*Cm annually with the capability of expansion to

20 kg annually. In this facility the source fabrication operations would be done in 11 in-line cells with material transfer ports in the cell dividing walls. Seven of the cells would be maintained under argon atmosphere during source fabrication operations. The nominal interior

8 dimensions of the cells are 7-ft wide by 8-ft deep by 11-ft vertical height above the work tray. The cost of equipment to be installed in the cells is estimated to be $600,000 including vacuum hot presses, calorimeters, welders, NDT instrumentation, furnaces, and speciallized tools and manipulators. For the 10 kg/year production level the cost of curium source fabrication is estimated to be $42/W , based on 10 sources requiring 1 kg of
2tft>

Cm each. This is a very preliminary estimate based on a single source

design concept with no detailed design or specifications; therefore, the actual cost can vary considerable from this depending on the actual source design and specifications. The fabrication facility would be capable of processing at greater rates with comparatively small increases in operating cost, assuming the complexity of source design does not increase. For a 20-kg/year throughput, the source fabrication is estimated to cost $28/W .

ORNL-DWG 65-7974R

HYDRAULIC CYLINDER

WATER COOLED BELLOWS WATER COOLED VACUUM JACKET PUNCH MOLYBDENUM HEAT REFLECTOR DIE BODY

SAMPLE HEATING ELEMENT PUNCH VIEWING PORT

WATER COOLED BASE

WATER-COOLED, THREADED ELECTRICAL CONDUCTORS

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