Materials Science and Engineering A357 (2003) 297 /303 www.elsevier.

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Application of cold crucible for melting of UO2/ZrO2 mixture

S.W. Hong *, B.T. Min, J.H. Song, H.D. Kim
Thermal-Hydraulic Safety Research Team, Korea Atomic Energy Research Institute, P.O. Box 105, Yusong, Daejon 305-600, South Korea Received 1 October 2002; received in revised form 5 March 2003

Abstract Using the cold crucible melting method, which has been found to be the best technique for the melt preparation of highly refractory materials, melting and discharge experiments for TiO2, ZrO2 and UO2/ZrO2 mixtures were conducted. The cold crucible, 15 cm in diameter and 20 cm in height, was used to get from 3 to 10 kg melts depending on the materials. Volatile gases generated during the melting period were well released through a hole of /2 cm in diameter and 10 cm in depth. The rubble crust layer with a gas vent hole, which is stably formed at the top of the melt, contributed to reduce the radiation loss from the melt surface. In reducing the thickness of the bottom crust, a partitioned plug is more effective than a solid plug, resulting in the easy achievement of the melt discharge. The most important factors for successful melting and discharge of refractory materials are the gas release hole and the plug shape. The developed melt discharge method was successfully applied to the fuel coolant interaction experiment using ZrO2 and UO2/ZrO2 mixtures. # 2003 Elsevier Science B.V. All rights reserved.
Keywords: Melting; Discharge; Cold crucible; Fuel-coolant interaction; UO2/ZrO2

1. Introduction For experiments to investigate the safety of nuclear power plants during severe accidents, such as Three Mile Island and Chernobyl, it is necessary to make a molten pool of the prototypic reactor material, whose typical composition is represented by a mixture of ZrO2 and UO2 [1]. As these materials have extremely high melting temperatures, it is very difficult to melt and handle the molten materials. The materials for the crucible should have a higher melting point than the material inside and should be chemically stable. Unfortunately, no satisfactory materials have yet been found. If we use a crucible made of molybdenum (melting point: 2700 8C) or tungsten (melting point: 3400 8C) for melting of UO2/ ZrO2 mixtures, it has the disadvantages of requiring multiple insulation layers to minimize heat losses and the accompanying unwanted contamination by chemical reaction [6]. In addition, if we use a direct electrical

* Corresponding author. Tel.: '/81-42-868-8997; fax: '/82-42-8612574. E-mail address: swhong@kaeri.re.kr (S.W. Hong).

heating method for the melting of UO2/ZrO2 mixtures, the melting efficiency is very low [7]. The cold crucible melting method [1] was used for the melting of highly refractory materials. This method is also called the skull melting method because the skull formed between the melt and the cold crucible acts as a self-container. It basically consists of an inductive heating of an electrically conducting melt by an alternating electromagnetic field. Heating is accomplished by ohmic losses caused by eddy currents induced in the melt itself. It has unique characteristics and specific applications. The great purity offered by the cold crucible [2,3] enable us to make gems by the crystal growth process. The advantage that the electro-magnetic force gives us, is a good mixing effect due to strong stirring [4], resulting in the levitation melting of the mixture of two metals with large density difference. Accordingly, the existing application of cold crucible melting has been limited to the melting of small amounts of materials for the purpose of crystal growth, levitation, and vitrification of radioactive material [2 /5]. In this paper, the process of developing a cold crucible technique for the melting of prototype reactor material and the results of experiments are discussed. The design parameters for selecting the frequency of the generator,

0921-5093/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0921-5093(03)00248-X

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determining the size of the crucible, and the development of the plug and puncher system for the discharge of the molten materials from the crucible are discussed. The materials used are TiO2, ZrO2, and a mixture of UO2/ZrO2.

2. Experiment To investigate the feasibility of the cold crucible melting and discharge technique for use in the fuel coolant interaction (FCI) experiment, where a jet of molten material should be discharged in a controlled manner to a test section containing water, a cold crucible system including a crucible, plug, and puncher were developed and tested. 2.1. Design parameters The size of the cold crucible is basically determined from the amount of molten material. The fact that powders contract when they reach the molten state should be considered in determining the height of the crucible. Fig. 1 shows the schematic diagram of the cold crucible that is designed to have a hole at the bottom to discharge the molten material. The frequency of the generator is chosen from the penetration depth, which is determined from the electrical resistivity of the melt. It is generally known that a length equivalent to /15% of the crucible diameter is suitable as a penetration depth for the cold crucible melting [8]. Fig. 2 shows the relation between electrical resitivity, penetration depth and frequency. The electrical resitivity of the molten UO2/ZrO2 (weight ratio 8:2) mixture is /4 )/10(3 V cm at its melting temperature [9]. If the diameter of the crucible is 10 cm, about 50 kHz in frequency can be selected for UO2/ZrO2 mixtures.

Fig. 2. Relation between PD and ER.

The heating efficiency in the cold crucible melting depends on the characteristics of the energy absorption. If the selected penetration depth is higher than proper penetration, melting efficiency decreases because most of the heat is lost to the crucible surface. If the selected penetration is smaller than the proper penetration, melting efficiency also decreases because electro-magnetic fluxes cross each other at the center of the crucible. The capacity of the maximum power input of the RF generator must be determined by considering the heat balance between the RF input power and the heat loss. The RF input power is consumed by the melt charge, crucible, and coil. The power input to the melt charge is balanced by the increase in the energy of the melt, radiation heat loss from the top of the charge, and heat loss to the crucible. It is difficult to determine the capacity of the RF power because we do not have much information for the thermal conductivity and the crust layer thickness, so the capacity is determined from the preliminary tests using TiO2. The capability of cooling has to be selected so that it can cool all the input power provided to the system. To discharge the melt into test section, two devices, a plug and a puncher, are designed. The plug, located at the bottom of the crucible, keeps the melt in the crucible during the melting period. Two kinds of plugs, as shown in Fig. 3, are designed and tested. The first one is a solid shape and the other is a partitioned type. The partitioned plug resulted in a

Fig. 1. Cold crucible shape.

Fig. 3. Plug shape.

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thinner bottom crust than that of solid plug due to better penetration of magnetic flux. The mechanism of plug operation is designed so that the plug can be closed and opened in upright position. The plug is taken out after the completion of melting. The molten material still does not discharge, as the sintered layer is between the molten pool and the inner surface of the crucible. A puncher is designed to perforate the bottom crust and discharge the melt. The puncher header, as shown in Fig. 4, has a conical shape to easily perforate the bottom crust. After the puncher perforates the bottom crust, it returns quickly to avoid contact with the melt. 2.2. Experimental facility and test results
Fig. 5. Schematic diagram for test facility.

Fig. 5 shows the schematic diagram for the test facility. The power of the RF generator is controlled from a PC. The outside wall of the cold crucible was wrapped with a bandage to prevent erupting the melt through the gaps between the copper tubes. Our final goal is to develop a cold crucible system to be used for the melting of the corium, which is a mixture of UO2 and ZrO2 at about 80:20 wt.%. In the first series of tests, TiO2 is used to investigate the general feasibility. After a successful test for TiO2, it was possible to determine the major design parameters for the cold crucible system and RF generator. Then, the second series of tests using pure ZrO2 was performed in a similar manner to those of TiO2. ZrO2 is used because its thermo-physical properties are close to those of corium and it is not radioactive. Finally, the test for the UO2/ ZrO2 mixture, which is very difficult to handle, as it is radioactive, was performed. 2.2.1. TiO2 melting and discharge test TiO2 melting and discharge tests were carried out in a cold crucible, which is 15 cm in diameter and 20 cm in height. The RF generator power was 30 kW and the frequency was 350 kHz. TiO2 in the form of powder was charged in the crucible. The initiator of the titanium metal ring was put into 2 /3 cm below the top of the charged powders. The size of coil is 24 cm in diameter and 17 cm in height with 8 turns. The lowest location of

the induction coil is about 6 cm from the bottom of the cold crucible.Within a few minutes of the initiation of the power supply, the melting of the TiO2 powders was started after the oxidation of the titanium metal ring. Reaction gas was released from the top surface of the melt. The TiO2 powder was sufficiently melted after / 30 min. A turbulent mixing of the melt was observed by the naked eye, as shown in Fig. 6. As the melt surface is directly exposed to the environment, a radiation heat loss seems to be higher than the heat loss to the crucible. A crust layer of 2/3 mm was formed between the molten pool of material and the inner surface of the cold crucible. To reduce the radiation loss from the melt surface in the TiO2 melting test, which decreases the efficiency of cold crucible melting, we made a cylindrical hole in 2/3 cm diameter at the center of the charged powder. Also, the bottom of the induction coil is descended /3 cm below the cold crucible bottom to increase the coupling between the melt and magnetic flux. The test result showed that the hole for gas vent, as shown in Fig. 7, plays a sufficient role in releasing gases generated during melting. The rubble crust that was formed over the melt (see Fig. 7) decreases the radiation loss and results in a increase in the efficiency.

Fig. 4. Conical puncher shape.

Fig. 6. Turbulent mixing.

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Fig. 7. TiO2 rubble crust.

At first, it was expected that the melt could be easily discharged instantly after opening the plug. However, the melt was not discharged through the hole due to the crust formed at the bottom of the crucible. So, we designed a puncher to penetrate the bottom crust. The melt was discharged through the hole after the actuation of the puncher. The size of the plug is about 6 cm, but the hole perforated by the puncher is only about 3 cm, as shown in Fig. 8. The black part of Fig. 8 shows that the bottom crust formed between the melt and water distribution chamber of the cold crucible. About 4.7 kg of mixture of TiO2 powder and solidified debris of previous experiments are initially charged into a crucible. 2.6 kg, about 60% of the initial charged mass was discharged. The rest remains in the crucible in the form of the rubble crust and the sintered layer along the inner surface of the crucible. 2.2.2. ZrO2 melting and discharge test For the ZrO2 and corium test, a new generator was designed, as discussed in the previous section. It has a capacity of 150 kW and frequency of 50 kHz. The ZrO2 melting and discharge test was performed in a same manner, as that of the TiO2 test. The crucible was filled with approximately 10 kg of ZrO2 powder. A zirconium metal ring was inserted for start-up. It has a dimension of 50 mm in diameter and 10 mm in height. It has a weight of 100 g. For the release of the reaction gas, a 2 /3 cm hole was provided at the center of the charged powder in 10-cm depth. The gas

was released through the hole very effectively. Fig. 9 shows the rubble debris crust layer that was formed on the top of the melt. It played the role of decreasing the radiation loss and resulted in the increase of power efficiency. Its shape is almost similar to that used in the TiO2 discharge test, as shown in Fig. 7. From some tests using a solid plug, it is found that the bottom crust is so thick, as shown in the right of Fig. 9, that it was very difficult to penetrate the bottom crust by a puncher. From the TiO2 melt discharge test, it was found that it is very important to have a thin bottom crust to make an easy discharge of molten jet. Abe et al. [10] pointed out that the thickness of bottom crust does not decrease even though the input power increases. So, we invented a partitioned plug, which increased the magnetic flux and decreased the thickness of the bottom crust near the plug region. After we used the partitioned plug, a thin crust layer was formed, as shown in Fig. 10. The 7 kg of ZrO2 melt was discharged through the large hole perforated by the puncher as shown in Fig. 10.

2.2.3. UO2/ZrO2 melting and discharge test For the UO2/ZrO2 (7:3 wt.%) melting and discharge test, the UO2 pellet and ZrO2 powder are charged into the crucible, as shown in Fig. 11. ZrO2 powder was charged at the bottom of the crucible to prevent an accidental release of the charged material. A zirconium metal ring, the initiator, was used because it becomes ZrO2 after oxidation. By using a segmented plug for the penetration of magnetic flux, a very thin crust of less than 2 mm thickness was formed between the melt and the cold crucible, as expected. As shown in Fig. 12, the melt could be easily discharged. Fig. 13 shows the operating condition of the RF generator for UO2/ZrO2 mixture melting. We can estimate the melting situation by checking the quality factor, Q , of the tank circuit. The equivalent circuit for the series resonance is shown in Fig. 14. Because the impedance of tank circuit, Z , is equal to the resistance of coil, Q can be written as

Fig. 8. Punched discharge hole for TiO2.

Fig. 9. ZrO2 rubble crust (top and bottom).

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Fig. 10. Bottom crust and punched hole for partitioned plug.

Fig. 13. RF operating curve.

Fig. 14. Equivalent electrical circuit model for the cold crucible.

can be expressed from Eq. (2) as

Fig. 11. UO2/ZrO2 mixture charging method.

Q0

Ac Vc Adc Vdc

(3)

Fig. 12. UO2/ZrO2 melt discharge picture.

Q0

vL ZL r Z

VL =IL V =I

(1)

where angular frequency v 0/2pf , r is coil resistance, L is reactance, ZL is impedance, VL is coil voltage and IL is coil current. From I0/IL, the Eq. (1) can be expressed as Q0 PL P : PC P (2)

where PL is tank coil power and PC is condenser power. In other words, the power applied to the tank condenser

where Vc(V ) and Ic(A ) are the condenser voltage and current (A), and Vdc(V ) and Adc(A ) are the coil voltage and current. The melting state can be predicted from the change of this Q value. The decrease of Q value means the increment of coil resistance by the resistance reflected from the load when power is applied to the coil. Because the electrical conductivity of the oxides increases with temperature, the magnetic energy can be absorbed by the induction of material itself, if a critical temperature was reached by the heating of the initiator. The temperature increases drastically by the absorption of the energy, so called coupling, and soon the material starts melting. The change of the RF coil current, voltage and Q value indicates coupling. Further change of the operating parameters shows the increase of melt size. By observing the trend of the coupling factor during the melting period, we can notice that when the materials reach the molten state. As the electrical conductivity of material rapidly increases near the melting point of the material, the induced current and resultant power absorption in the melt increases rapidly near the melting point of material. We know materials reached the molten state at /1800 s from Fig. 15. From Kirchoffs voltage law, the electrical equivalent circuit of the skull melting system is shown in Fig. 16 [5]. The input power distribution is calculated as:

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S.W. Hong et al. / Materials Science and Engineering A357 (2003) 297 /303 Table 1 Measured current and voltage DC current (A) Coil Coil'/crucible 50 100 50 100 DC voltage (V) 38 74 96 198 Power (kW) 1.9 7.4 4.8 19.8

(Pmel) is calculated by subtracting the induction coil and crucible loss from total input power (Psys). It can also be calculated from the following equation using a measured coupling factor,
Fig. 15. Power absorption to each component.

Pmel 0hPsys where h0 Qi ( Qf Qi

(5)

(6)

Fig. 16. SEM picture.

2 2 Ptot 0Ico R 0Ico (Rco 'Rcru 'Rme )

0I(Vco 'Vcru 'Vme )

(4)

where Ico is coil current (A), and V and R are the voltage (V) and electrical resistance (V), respectively, to each component. To calculate input power distribution to the induction coil, the crucible and the melt, the voltage to each component should be known for the specified current. The loss through the coil can be determined by measuring the voltage drop without installing the crucible. Then, the loss from the crucible is calculated by subtracting the induction coil loss from total input power, which can be measured by installing the crucible without melt and a induction coil. Table 1 shows the measured voltage and current. When only the induction coil is installed, coil voltage to the induction coil was measured at 50 and 100 A. Coil voltage is also measured under the installation of the induction coil and crucible without melt for the same currents. Heat losses to the coil and crucible for other currents can be easily calculated because the voltage is proportional to the current, as shown in Table 1. As the coil current and voltage can be measured during the melting period, the power applied to the melt

where Qi is the initial coupling factor and Qf is the coupling factor under steady state as shown in Fig. 15. The power distribution was calculated for the UO2/ ZrO2 melting and discharge test. The heat absorption to the melt appeared to be almost the same in the two methods. Fig. 15 shows the heat losses for the total experiment period. About 55 and 25% of the applied power are absorbed in the melt and crucible, respectively. Chemical analysis is performed to see the composition change of the initial UO2 and ZrO2 mixture. The mixture after reaction with the water is reduced at the hydrogen atmosphere during 12 h at 1700 8C. It is judged that UO2 does not changed into the UO22'x or U3O8 because the weight of the initial mixture after the reduction is equally maintained. And the mixture is oxidized in the air from 20 to 1000 8C (10 8C min (1) by the TG (Thermogarvimetry/Differential Thermal Analysis) method. After oxidation, the weight of initial mixture, 59.5 mg, is increased by 2% in weight, 1.19 mg. This result is caused by the oxidation of UO2 to U3O8. Fig. 16 shows SEM picture. The black part shows the uniform mixture and the white point shows the part that contains relatively large fraction in ZrO2.

3. Results and discussion From the TiO2 melting and discharge tests, it is suggested that the cold crucible melting could be applied to the FCI test. However, it had a problem that the melt is not discharged easily because of a thick bottom crust formed at the bottom of the crucible. In the ZrO2 discharge tests, a partitioned plug is invented and it was found that it was very effective in maintaining a thin crust at the bottom. A ZrO2 melt discharge test was

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applied to our FCI test. The UO2/ZrO2 melt discharge test using the partitioned plug was also successfully performed and applied to our FCI test. The power distribution to coil, crucible and melt was also analyzed. About 55% of the total power was absorbed in the melt and the rest of it was lost to the coil and crucible. For UO2/ZrO2 melting and discharge for FCI tests, it is thought that the developed method using cold crucible melting is easier than existing methods.

Acknowledgements This project has been carried out under the Nuclear R&D Program by MOST.

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