The present invention relates to nuclear fuel pellets and a manufacturing method thereof, and more particularly, to nuclear fuel pellets comprising a trapping material of fission gas and a manufacturing method thereof.
Starting from the Fukushima nuclear disaster, accident tollerant fuel (ATF) for improving the stability of nuclear fuel has been actively developed. As part thereof, the development of fission gas release (FGR) improved pellets has been conducted to reduce fission gas (FG) generated in nuclear fuel pellets during operation of a nuclear reactor from being released to the outside of the pellets. Cesium (Cs) and iodine (I) are main fission gases that threaten the safety problem of the nuclear fuel in terms of the generation amount and toxicity thereof due to a high radioactivity level and high absorption in the human body because the cesium (Cs) and iodine (I) may be present as gases.
To this end, a Cs trapping material has been developed based on a SiO2-based material, and recently, the development of trapping materials capable of stably trapping and storing Cs even in an accident situation according to an ATF development purpose has been conducted.
Meanwhile, in a nuclear fuel rod for a nuclear power plant, many nuclear fuel pellets are laminated in a cladding tube, and as a nuclear reaction is performed in a nuclear reactor, the nuclear fuel pellets are volume-expanded to reduce a distance between the nuclear fuel pellets and the cladding tube, and as a result, the nuclear fuel pellets are in contact with each other to give stress to the cladding tube. In addition, gas with strong corrosion is generated due to a nuclear reaction product to increase an internal pressure, and as a result, stress corrosion cracking (SCC) occurs due to physical and chemical interactions between the nuclear fuel pellets and the cladding tube. The iodine (I) of the fission gases has a small generation amount as compared with Cs, but is one of gases that cause SCC to the cladding tube, but the development of a trapping material to I is very slight.
In other fields, many studies for trapping for I have been conducted, but these processes mainly have wet processes such as Mercurex and Iodox, and as a result, it is difficult to be applied to the field consisting of a series of dry processes. In addition, through the same hot sintering process as when manufacturing the nuclear fuel pellets, there is a problem that a trapping material developed in the related art also losses a trapping function for I, and there is almost no case of developing a trapping material capable of a selective trapping ability for I as fission gas.
In the conventional Cs trapping material, there is proposed a technique of trapping I in the form of CsI as a trapping product using a trapping material pre-trapped with Cs, but in the corresponding technique, first, since I is trapped as the trapping product in the form of CsI, in order to trap I, since there is required a prerequisite that the Cs needs to be pre-trapped, there is a problem that a trapping probability of I itself is lowered. That is, when Cs and I are diffused independently in base particles, respectively, there is a problem that I cannot be trapped with a trapping material itself which is not trapped with Cs. In addition, since CsI as the trapping product is not excellent in stability at a high temperature due to a melting point of about 621° C., the trapping using the above composition is not useful even in that I can be trapped only in a very partial area with a low temperature in the nuclear fuel pellets. In addition, a conventional trapping material itself trapped with Cs may be stably preserved in a grid up to a high temperature to stably preserve Cs up to a high temperature. However, when I is trapped using the trapping material trapped with Cs, Cs which has been trapped in the trapping material reacts with I to form a CsI phase and volatilized to gas at a lower temperature, and rather, there is a problem that the CsI phase adversely affects Cs trapping.
Accordingly, even while the trapping ability for fission gas such as Cs and I is excellent, the demand on the development of nuclear fuel pellets having a independent trapping ability for each of Cs and I and a manufacturing method thereof has continued.
An object of the present invention is to provide nuclear fuel pellets with improved FGR for preventing the volatilization of fission gas and facilitating the removal of fission gas by trapping fission gas, and a manufacturing method thereof.
Specifically, an object of the present invention is to provide nuclear fuel pellets having an independent trapping ability for each of Cs and I with excellent trapping abilities for Cs and I as fission gases, and a manufacturing method thereof.
In order to achieve the object, the present invention provides a nuclear fuel pellet comprising a nuclear fuel; and a trapping material of fission gas, wherein the trapping material of the fission gas includes an oxide containing at least one element selected from the group consisting of silicon (Si), aluminum (Al) and barium (Ba).
In addition, the present invention provides a manufacturing method of a nuclear fuel pellet comprising mixing and then sintering a nuclear fuel raw material; and at least one oxide selected from the group consisting of a silicon oxide, an aluminum oxide, and a barium oxide.
The nuclear fuel pellets of the present invention may exhibit an excellent trapping effect on fission gases. Specifically, the nuclear fuel pellet of the present invention may selectively trap and separate Cs and/or I of fission gases, and more particularly, may exhibit an independent trapping ability for Cs and I. Accordingly, as compared with a conventional I trapping technique in which Cs trapping is a prerequisite, I may be trapped independently of the Cs trapping to improve the trapping efficiency of I. In addition, since an interference effect by I is reduced, the Cs trapping efficiency may also be improved, and since the Cs trapping product is preserved at a higher temperature, the volatilization rate of Cs and I may be significantly reduced.
In addition, when the nuclear fuel pellets of the present invention are used, Cs and/or I as fission gas is selectively trapped in the pellets, and thus, there is an advantage of alleviating the rise of a rod internal pressure during a normal operation and lowering the SCC occurrence rate of the cladding tube. Accordingly, even while the nuclear fuel is exposed due to a nuclear accident, it is possible to prevent or delay FG from being emitted to an environment within a trapping temperature range.
In addition, by using the manufacturing method of the nuclear fuel pellets of the present invention, it is possible to manufacture nuclear fuel pellets having an excellent trapping effect for fission gases, specifically, a selective trapping ability for Cs and/or I of fission gases and an excellent trapping ability independently of each of the Cs and/or I.
The accompanying drawings of this specification exemplify a preferred embodiment of the present invention, the spirit of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, and thus it will be understood that the present invention is not limited to only contents illustrated in the accompanying drawings.
BaO*Al2O3+2Cs(g)+2SiO2+½O2(g)=2CsAlSiO4+BaO A1:
BaAl2O4+2Cs(g)+2SiO2+½O2(g)=2CsAlSiO4+BaO A2:
Al2O3*SiO2+2Cs(g)+SiO2+½O2(g)=2CsAlSiO4 A3:
BaSiO3+2Cs(g)+½O2(g)=Cs2O*SiO2+BaO A4:
Al2O3+2Cs(g)+2SiO2+½O2(g)=2CsAlSiO4 A5:
BaO*Al2O3+I2(g)=BaI2+Al2O3+½O2(g) B1:
BaAl2O4+2I2(g)=BaI2+Al2O3+½O2(g) B2:
BaSiO3+I2(g)=BaI2+SiO2+½O2(g) B3:
BaAl2SiO8+I2(g)=BaI2+Al2O3+2SiO2+½O2(g) B4:
A nuclear fuel pellet of the present invention comprises a nuclear fuel; and a trapping material of fission gas, wherein the trapping material of the fission gas includes an oxide containing at least one element selected from the group consisting of silicon (Si), aluminum (Al) and barium (Ba).
The nuclear fuel may be an uranium-based oxide, and for example, may be uranium dioxide (UO2), triuranium octoxide (U3O8), or a mixture thereof. More specifically, the nuclear fuel may be UO2.
The trapping material of the fission gas comprises an oxide containing at least one element selected from the group consisting of silicon (Si), aluminum (Al), and barium (Ba). In an embodiment, the trapping material of the fission gas may be formed by sintering at least one oxide selected from the group consisting of a silicon oxide, an aluminum oxide, and a barium oxide, and specifically, the trapping material of the fission gas may include an oxide containing silicon, aluminum, and barium. The trapping material of the fission gas includes an oxide containing at least one element selected from the group consisting of silicon, aluminum, and barium, specifically an oxide containing silicon, aluminum, and barium to exhibit a trapping ability independently with respect to each of cesium and iodine.
The nuclear fuel pellet according to the present invention includes barium in the trapping material composition to exhibit an excellent trapping ability for I, as compared with a conventional trapping material of an oxide composition (Al—Si—O composition) containing silicon and aluminum having a trapping ability for Cs.
The trapping material of the fission gas is not limited thereto, but may be included in a grain boundary of the nuclear fuel pellet. As illustrated in
In addition, in an aspect, the amount of the trapping material of the fission gas in the nuclear fuel pellet may be 0.05 to 1 wt %, for example, 0.1 to 0.5 wt % with respect to the weight of the nuclear fuel, but is not limited thereto.
In an aspect, it was confirmed that the amount of the trapping material of the fission gas estimated by measuring the amount of the fission gas trapped using the nuclear fuel pellet was 0.15 wt % with respect to the total weight of the nuclear fuel (ex. UO2).
The fission gas may include at least one selected from the group consisting of cesium (Cs) and iodine (I) and specifically, may include at least one selected from the group consisting of cesium and iodine. More specifically, the nuclear fuel pellet according to the present invention may exhibit an independent trapping ability for cesium and iodine while the trapping ability for each of cesium and iodine is selectively excellent. In addition, the trapping product is not limited thereto, but for example, CsAlSiO4, CsAlSi2O6 and BaI2 of the trapping products may exhibit a high trapping rate for Cs and I in a wider area in the nuclear fuel due to relatively high melting points.
As described above, the trapping material of the fission gas may comprise an oxide containing at least one element selected from the group consisting of Si, Al and Ba. In addition, in an aspect, the oxide includes a compound represented by the following Formula 1 to exhibit an excellent trapping ability independently for each of Cs and I.
BaxAlySizOw (wherein, 0≤x≤2, 0≤y≤2, 0≤z≤3, and 0<w≤8, and 2x+3y+4z=2w.) [Formula 1]
Preferably, the oxide includes a compound represented by the following Formula 2 to exhibit an excellent trapping ability independently for each of Cs and I.
BalAlmSinOp (wherein, 0<l≤2, 0<m≤2, 0<n≤3 and 0<p≤8, and 2l+3m+4n=2p.) [Formula 2]
In an aspect, the trapping material of the fission gas may include an oxide in the form of BaAl2Si2O8.
The nuclear fuel pellet includes the trapping material of the Ba—Al—Si—O composition as described above to exhibit an effect capable of independently trapping I as a trapping product in the form of BaI2. Accordingly, as compared with a conventional I trapping technique using a Cs trapping product in the form of CsAlSiO4, CsAlSi2O6, and the like, the nuclear fuel pellet may exhibit an excellent effect of preventing diffusion for Cs and I by stably trapping Cs without separating Cs from the trapping product.
The trapping material of the fission gas in the nuclear fuel pellet is not limited thereto, but for example, an average particle size (D50) may be 0.1 to 100 μm, specifically 10 to 50 μm.
A manufacturing method of the nuclear fuel pellet of the present invention includes mixing and then sintering a nuclear fuel raw material; and at least one oxide selected from the group consisting of a silicon oxide, an aluminum oxide, and a barium oxide.
The nuclear fuel raw material may be an uranium-based oxide, and specifically, may be a uranium oxide or a compound formed by mixing at least one selected from the group consisting of a plutonium oxide, a gadolinium oxide, and a thorium compound with the uranium oxide.
At least one oxide selected from the group consisting of a silicon oxide, an aluminum oxide, and a barium oxide which is mixed with the nuclear fuel raw material is a raw material for forming the trapping material of the fission gas. A mixed weight ratio of the nuclear fuel raw material and the oxide is not limited thereto, but for example, may be 0.05 to 1 wt % with respect to the total weight of the nuclear fuel raw material. As an example, the nuclear fuel pellet manufactured when the mixed weight ratio of the nuclear fuel raw material and the oxide is mixed in the range to manufacture the nuclear fuel pellet has an appropriate density range and may exhibit an excellent reactivity effect while exhibiting an excellent trapping ability for the fission gas. 0.05 wt % of a lower limit of the range is based on a minimum required amount calculated to trap Cs and I generated within the nuclear fuel, and 1 wt % of an upper limit is based on a maximum added amount (as the added amount is increased, the sintering density is reduced) capable of satisfying a sintering density (relative density of about 95%) reference as the nuclear fuel, respectively.
In the manufacturing method of the nuclear fuel pellet of the present invention, when the nuclear fuel raw material, the silicon oxide, the aluminum oxide, and the barium oxide all are mixed, the mixed weight ratio thereof is set so that there is a phase in which the generated trapping material spontaneously traps Cs and I, and is not particularly limited thereto.
In an embodiment, as a result of manufacturing the nuclear fuel pellet using a mixture of the silicon oxide, the aluminum oxide, and the barium oxide at a weight ratio of 1:1:1, it was confirmed that the nuclear fuel pellet exhibits an excellent trapping ability for Cs and I (
In the step of mixing and then sintering the nuclear fuel raw material and the oxide, the sintering may be performed under a reducing gas atmosphere, and the reducing gas atmosphere may include hydrogen and inert gas atmospheres. The sintering atmosphere may be generally performed under a sintering condition of the manufacturing method of the nuclear fuel pellet and an additional optimization process is not required and it is economic.
In addition, the sintering may also be performed at a temperature which is higher than an eutectic temperature of the nuclear fuel raw material and the oxide for forming the trapping material of the fission gas and lower than a melting temperature of each of the nuclear fuel raw material and the oxide. The sintering is performed at a temperature higher than the eutectic temperature of the nuclear fuel raw material and the oxide to form grains and grain boundaries, preferably a trapping material of the fission gas in the grain boundaries, thereby improving a problem of reducing the trapping ability of the nuclear fuel pellet due to the volatilization of the trapping material. Accordingly, it is possible to improve the durability of the nuclear fuel pellet.
Hereinafter, the present invention will be described in detail with reference to Examples for understanding. However, Examples according to the present invention may be modified in various forms, and it is not interpreted that the scope of the present invention is limited to the following Examples. Examples of the present invention will be provided for more completely explaining the present invention to those skilled in the art.
Manufacturing of Nuclear Fuel Pellets and Confirmation of Microstructure
The manufacturing of nuclear fuel pellets was performed in order of preparation of starting powder, powder weighing, mixing, molding, and sintering. Al2O3, SiO2 and BaO powders as the starting powder were weighed according to a weight ratio to be mixed with UO2 powder. The mixing was performed for 30 minutes to 2 hours using a turbula mixer to secure uniformity. The mixed powder was introduced to a metal mold for molding to be pressed in a pellet form by applying pressure of 1 to 5 ton/cm2 using a uniaxial molder. The molded pellets were introduced into a ceramic furnace and mounted in a heat-treatment furnace and then a reducing atmosphere was formed using hydrogen and carbon dioxide gases in a chamber and then isothermal sintering was performed for several times within about 1700° C. At this time, in order to minimize the heat shock of the sintering pellets, heating and cooling rates were within 5° C./min.
The microstructure of the nuclear fuel pellet may be checked by an optical microscope, an SEM, and the like. The pellet was cut in an axial direction or radial direction using a diamond saw to expose the inner surface of the sintered pellet and then mount the corresponding surface to be exposed using a resin. When the curing of the resin was completed, the cutout surface of the sintered pellet was polished using a polisher. The polishing was performed in order from rough polishing that held a side surface to fine polishing using a diamond paste, and the surface was observed with an optical microscope after the polishing was finished (
Equilibrium Composition Analysis of Trapping Material
A result of predicting an equilibrium composition of a trapping material prepared by weighing Al2O3, SiO2 and BaO powders at a weight ratio of 1:1:1 and using the powders as starting powders using HSC chemistry was illustrated in
In order to verify spontaneous trapping performance for Cs and I reaction specimens using the trapping material prepared by weighing Al2O3, SiO2 and BaO powders prepared above at the weight ratio of 1:1:1, the potentials of a Cs trapping product and an I trapping product formed from the equilibrium phases were calculated and the result thereof was illustrated in
According to the results of
In order to verify trapping performance for Cs and I reaction specimens using the trapping material prepared by weighing Al2O3, SiO2 and BaO powders prepared above at the weight ratio of 1:1:1, as an example, a reaction heat-treatment experiment was performed at a reducing atmosphere at 650° C.
After reacting gas-phase Cs and I with the compound of the Ba—Al—Si—O composition through heat treatment, respectively, as a result analyzed by XRD and SEM/EDS, it was confirmed that in the Cs reaction specimen, CsAlSiO4 and CsAlSi2O6 were observed (
Number | Date | Country | Kind |
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10-2019-0047415 | Apr 2019 | KR | national |
Filing Document | Filing Date | Country | Kind |
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PCT/KR2020/004522 | 4/2/2020 | WO | 00 |