A kind of inertia base disperse pellet fuel and its preparation method and application
Technical field
The present invention relates to a kind of inertia base disperse pellet fuels and its preparation method and application.
Background technique
Nuclear power has the characteristics that safe and reliable, low-carbon cleaning, is the important component of future global energy structure.At present
Construction of Nuclear Electricity is being actively pushed forward in countries in the world, so that alleviating energy crisis, improves climatic environment.Fukushima, Japan " 311 " core thing
After therefore, traditional UO2The security risk that+Zr alloy fuel component is exposed in the state of accident has caused the strong of various countries
Concern.Traditional fuel component is improved, promoting the safety of nuclear fuel in the state of accident becomes worldwide research hotspot.?
Under this background, the concept of accident fault tolerant fuel (ATF) is come into being.ATF is to improve fuel element and resist under major accident
Performance and the fuel concept of new generation that proposes, in particular to: with current UO2+ Zr fuel phase transformation, can be in a long time
It resists coolant loss accident, be also able to maintain or improve it in the fuel system of accidental conditions performance simultaneously.The hot spot of ATF
One of research direction is to develop the excellent fuel pellet of high thermal conductivity, security performance.
IMDP has the characteristics that anti-radiation performance is excellent, fission gas inclusiveness is good, thermal conductivity is high, is a kind of security performance
Splendid fuel pellet.U.S.'s Oak Ridge National Laboratory is prepared for by hot pressing sintering method using SiC as inertial base, with
TRISO particle is the fine and close IMDP of fuel element.However the hot pressing sintering method sintering period is long, it is difficult to realize that industrial mass is raw
It produces.
Summary of the invention
The technical problem to be solved by the present invention is providing a kind of inertia base disperse pellet fuel, which has Flouride-resistani acid phesphatase
It has excellent performance, the feature that fission gas inclusiveness is good, thermal conductivity is high, security performance is excellent;A kind of inertia base is additionally provided simultaneously
The preparation method of disperse pellet fuel, the preparation method prepare IMDP using the method for pressureless sintering, are realizing the same of densification
When greatly improve preparation and production efficiency, realize can industrial mass production purpose;And then additionally provide inertia base disperse
Pellet fuel can be used as the purposes of water-water reactor and the fuel assembly for melting salt heap in nuclear reactor.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of inertia base disperse pellet fuel including fuel region and is coated on protecting without fuel region for the fuel region periphery
Layer, the fuel region include inertial base and the fuel element that is uniformly distributed in the inertial base, and the inertial base is
Fine and close SiC, the fuel element are TRISO coated fuel particles, and the no fuel region protective layer is made of SiC.
Further, the lazy base and the consistency without flame-proofing protective layer are not less than 96%.
Further, the TRISO coated fuel particles include fuel core and be coated on outside the fuel core four
Layer protective layer, four layers of protective layer are followed successively by loose carbon-coating, internal layer pyrolytic carbon layer, SiC layer and outer layer pyrolytic carbon from inside to outside
Layer;The fuel core is UO2、UC、UC2, one or more of UN, U alloy or other nuclear fuels, and the UO2、UC、
UC2, in UN, U alloy or other nuclear fuels235U degree of enrichment is 2-20%, and the density of the loose carbon-coating is 1.1g/cm3, thickness
It is 95 μm, the density of the internal layer pyrolytic carbon layer is 1.9g/cm3, with a thickness of 40 μm, the density of the SiC layer is 3.18g/cm3、
With a thickness of 35 μm, the density of the outer layer pyrolytic carbon layer is 1.9g/cm3, with a thickness of 40 μm;The TRISO coated fuel particles
Diameter be 500 μm.
Further, it is 30-60%, the no combustion that the TRISO coated fuel particles, which account for the volume fraction of pellet fuel,
Expect area's protective layer with a thickness of 0.2-2mm.
A kind of preparation method of inertia base disperse pellet fuel, comprising the following steps:
Step 1: preparation SiC mixed slurry and SiC mixed-powder;
Step 2: the SiC mixed slurry is coated on TRISO particle by spray deposition;
Step 3: the TRISO particle die forming of SiC will have been coated, obtained fuel region biscuit;
Step 4: by the SiC mixed-powder die forming, obtaining no fuel region biscuit;
Step 5: by the fuel region biscuit and without fuel region biscuit compound suppressing at IMDP biscuit;
Step 6: the IMDP biscuit is subjected to pressureless sintering in vacuum drying oven;
Step 7: by the pellet fuel of sintered blank machine addition final size.
Specifically, the sum of gross mass percentage composition of the SiC mixed slurry is based on 100%, including following component:
80-96wt.%SiC, 1-8wt.%Y2O3, 1-10wt.%Al2O3, 0-8wt.%SiO2With 0.5-2wt.% polyethyleneimine;Its
The partial size of middle SiC is 10nm-50 μm, Y2O3Partial size be 20nm-20 μm, Al2O3Partial size be 10nm-30 μm, SiO2Partial size
It is 10nm-50 μm, the molecular weight of polyethyleneimine is 800-1800;
Said components are placed in nylon ball grinder, in terms of the gross mass of said components, add the 1-2 times of gross mass
Alcohol mixing, the zirconium oxide abrasive ball or alumina ceramic grinding ball ball milling that 3 times of gross masses are added obtain SiC mixed slurry for 24 hours;
The SiC mixed slurry is drying to obtain SiC mixed-powder.
Specifically, the operation temperature of the step 2 is 70~100 DEG C;The pressing pressure being molded in the step 3 is 20
~60MPa, gained fuel region biscuit are column;The pressing pressure that the step 4 is molded is 20~60MPa, and gained is without fuel region
Biscuit includes upper and lower covers and cyclic annular cylinder, and with a thickness of 2-4mm, the fit clearance with the fuel region biscuit is 0.1-0.25mm;Institute
State the pressing pressure that the pressure of compound suppressing in step 5 is higher than the pressing pressure being molded in step 3 and is molded in step 4.
Specifically, the pressure of compound suppressing is 60~80MPa in the step 5.
Specifically, be warming up to 600 DEG C in the step 6 first with the rate of 5-10 DEG C/min and keep the temperature 0.5-2h, into
Row ungrease treatment, vacuum degree 10-2- 10Pa passes to argon gas protection, pressure 10-50kPa, with the rate liter of 2-10 DEG C/min later
Temperature keeps the temperature 1-5h to 1700-1900 DEG C, and furnace is cold.
Based on above description, the present invention also provides the inertia base disperse pellet fuels according to water-water reactor fuel in nuclear reactor
The size of component melts the purposes that salt heap fuel assembly is dimensioned to fuel ball.
Compared with prior art, the invention has the following advantages:
(1) present invention uses SiC, Y2O3、Al2O3、SiO2SiC mixed slurry and SiC mixing are prepared into polyethyleneimine
SiC mixed slurry is coated on TRISO particle by spray deposition and forms densification SiC inertial base to be made by powder
SiC mixed-powder is molded into no fuel region biscuit by fuel region biscuit, then by fuel region biscuit and without the compound pressure of fuel region biscuit
IMDP biscuit is made, IMDP biscuit is subjected to pressureless sintering at high temperature in vacuum drying oven later, by sintered blank by wanting after black furnace
Ask size by being machined into water-water reactor and melting the fuel assembly in salt heap;The present invention is prepared using the method for pressureless sintering
IMDP greatly improves preparation and production efficiency while realizing densification, effectively realizes the purpose of industrial mass production.
(2) IMDP main component of the present invention include the TRISO particle of 30~60vol.%, densification SiC inertial base and
Without fuel region protective layer, TRISO particle is with one or more of UO2, UC, UC2, UN, U alloy or other nuclear fuels for fuel
Core, from inside to outside successively by loose carbon-coating, internal layer pyrolytic carbon layer, SiC layer and external pyrolytic carbon layer composition;Fine and close SiC inertia
Matrix and SiC are higher than 96%, TRISO particle integrity degree without fuel region protective layer consistency and keep good, fine and close SiC inertial base
Close with TRISO interface cohesion, IMDP of the present invention has good heating conduction and core anti-radiation performance, enough mechanical strengths
With excellent fission gas inclusiveness, relative to the fuel assembly of traditional UO2 pellet+Zr alloy, safety has obtained significantly mentioning
It rises, can be used for water-water reactor and melts the fuel assembly in salt heap, there is extensive industrial prospect.
Detailed description of the invention
Fig. 1 is IMDP structural schematic diagram of the present invention.
Fig. 2 is preparation method flow chart of the present invention.
Specific embodiment
The invention will be further described with embodiment for explanation with reference to the accompanying drawing, and mode of the invention includes but not only limits
In following embodiment.
As shown in Figure 1, a kind of inertia base disperse pellet fuel of the invention, including fuel region and it is coated on the fuel region
Periphery without fuel region protective layer, the fuel region include inertial base and be uniformly distributed in the inertial base fuel member
Part, the inertial base be densification SiC, the fuel element be TRISO coated fuel particles, the no fuel region protective layer by
SiC is made.
The inertial base and consistency without fuel region protective layer are not less than 96%, the TRISO coated fuel particles
Including fuel core and four layers of protective layer being coated on outside the fuel core, four layers of protective layer is followed successively by thin from inside to outside
Loose carbon-coating, internal layer pyrolytic carbon layer, SiC layer and outer layer pyrolytic carbon layer;The fuel core is UO2、UC、UC2, UN, U alloy or its
One or more of his nuclear fuel, and the UO2、UC、UC2, in UN, U alloy or other nuclear fuels235U degree of enrichment is 2-
20%, the density of the loose carbon-coating is 1.1g/cm3, with a thickness of 95 μm, the density of the internal layer pyrolytic carbon layer is 1.9g/cm3、
With a thickness of 40 μm, the density of the SiC layer is 3.18g/cm3, with a thickness of 35 μm, the density of the outer layer pyrolytic carbon layer is
1.9g/cm3, with a thickness of 40 μm;The diameter of the TRISO coated fuel particles is 500 μm.
The volume fraction that the TRISO coated fuel particles account for pellet fuel is 30-60%, the no fuel region protective layer
With a thickness of 0.2-2mm.
IMDP main component of the present invention includes the TRISO particle of 30~60vol.%, densification SiC inertial base and without combustion
Expect area's protective layer, TRISO particle is with one or more of UO2, UC, UC2, UN, U alloy or other nuclear fuels for fuel kernel
The heart, from inside to outside successively by loose carbon-coating, internal layer pyrolytic carbon layer, SiC layer and external pyrolytic carbon layer composition;Fine and close SiC inertia base
Body and SiC are higher than 96%, TRISO particle integrity degree without fuel region protective layer consistency and keep good, fine and close SiC inertial base with
TRISO interface cohesion is close, and IMDP of the present invention has good heating conduction core anti-radiation performance, enough mechanical strengths and excellent
Different fission gas inclusiveness, relative to the fuel assembly of traditional UO2 pellet+Zr alloy, safety is obviously improved, can
For water-water reactor and melt the fuel assembly in salt heap, there is extensive industrial prospect.
As shown in Fig. 2, a kind of preparation method of inertia base disperse pellet fuel of the present invention, comprising the following steps:
Step 1: preparation SiC mixed slurry and SiC mixed-powder;
Step 2: the SiC mixed slurry is coated on TRISO particle by spray deposition;
Step 3: the TRISO particle die forming of SiC will have been coated, obtained fuel region biscuit;
Step 4: by the SiC mixed-powder die forming, obtaining no fuel region biscuit;
Step 5: by the fuel region biscuit and without fuel region biscuit compound suppressing at IMDP biscuit;
Step 6: the IMDP biscuit is subjected to pressureless sintering in vacuum drying oven;
Step 7: by the pellet fuel of sintered blank machine addition final size.
The sum of gross mass percentage composition of the SiC mixed slurry is based on 100%, including following component: 80-96wt.%
SiC, 1-8wt.%Y2O3, 1-10wt.%Al2O3, 0-8wt.%SiO2With 0.5-2wt.% polyethyleneimine;The wherein grain of SiC
Diameter is 10nm-50 μm, Y2O3Partial size be 20nm-20 μm, Al2O3Partial size be 10nm-30 μm, SiO2Partial size be 10nm-50 μ
M, the molecular weight of polyethyleneimine are 800-1800;
Said components are placed in nylon ball grinder, in terms of the gross mass of said components, add the 1-2 times of gross mass
Alcohol mixing, the zirconium oxide abrasive ball or alumina ceramic grinding ball ball milling that 3 times of gross masses are added obtain SiC mixed slurry for 24 hours;
The SiC mixed slurry is drying to obtain SiC mixed-powder.
The operation temperature of the step 2 is 70~100 DEG C;The pressing pressure being molded in the step 3 is 20~60MPa,
Gained fuel region biscuit is column;The pressing pressure that the step 4 is molded is 20~60MPa, and gained includes without fuel region biscuit
Upper and lower covers and cyclic annular cylinder, with a thickness of 2-4mm, the fit clearance with the fuel region biscuit is 0.1-0.25mm;In the step 5
The pressing pressure that the pressure of compound suppressing is higher than the pressing pressure being molded in step 3 and is molded in step 4.
The pressure of compound suppressing is 60~80MPa in the step 5, in the step 6, first with the speed of 5-10 DEG C/min
Rate is warming up to 600 DEG C and keeps the temperature 0.5-2h, carries out ungrease treatment, vacuum degree 10-2- 10Pa passes to argon gas protection, pressure later
10-50kPa is warming up to 1700-1900 DEG C with the rate of 2-10 DEG C/min, keeps the temperature 1-5h, and furnace is cold.
The present invention uses SiC, Y2O3、Al2O3、SiO2SiC mixed slurry and SiC mixed powder are prepared into polyethyleneimine
SiC mixed slurry is coated on TRISO particle by spray deposition and forms densification SiC inertial base to which combustion be made by end
Expect area's biscuit, SiC mixed-powder is molded into no fuel region biscuit, then by fuel region biscuit and without fuel region biscuit compound suppressing
At IMDP biscuit, IMDP biscuit is subjected to pressureless sintering at high temperature in vacuum drying oven later, after black furnace as required by sintered blank
Size is by being machined into water-water reactor and melting the fuel assembly in salt heap;The present invention prepares IMDP using the method for pressureless sintering,
Preparation and production efficiency are greatly improved while realizing densification, effectively realizes the purpose of industrial mass production.
Using the inertia base disperse pellet fuel of this preparation method preparation finally according to water-water reactor fuel assembly in nuclear reactor
Size or melt the size of salt heap fuel assembly water-water reactor just can be processed into using purely mechanic method and melt the fuel assembly of salt heap.
In order to be further elaborated to the present invention, several preferred embodiments presented below.
Embodiment 1:
Step 1: weighing each powder: SiC, 10nm, 80wt.% in following specification and ratio;Y2O3, 20nm, 8wt.%;
Al2O3, 10nm, 10wt.%;Polyethyleneimine, molecular weight 800,2wt.%.By above-mentioned powder with etc. quality alcohol mix, be placed in
In nylon ball grinder, mill ball uses zirconia ball, ratio of grinding media to material 3:1, and ball milling obtains SiC slurry for 24 hours.By the slurry equal part, one
Part is for coating TRISO particle;Another is dried for 24 hours at 80 DEG C, and SiC mixed-powder is obtained after sieving.
Step 2: SiC mixed slurry is coated on TRISO particle by spray deposition.TRISO particle is placed on
It is rolled on vibrator, and imposes 70 DEG C of temperature.Using the SiC slurry prepared in step 1, mist is formed by spray generator
SiC powder is deposited on TRISO particle surface by shape slurry.Angle, size of dehiscing, spraying pressure by adjusting spray generator
The parameters such as power, flow velocity modulate suitable atomizing effect.By coating the SiC mixed-powder of different quality, can be obtained different
TRISO volume fraction.
Step 3: the TRISO particle die forming of SiC will have been coated, obtained fuel region biscuit.It is wanted according to fuel region size
Ask carry out mold design, and the die forming under the pressure of 20MPa.
Step 4: by SiC mixed-powder die forming, obtaining no fuel region biscuit.No fuel region biscuit include upper and lower covers and
Cyclic annular cylinder, with a thickness of 2mm, the fit clearance with fuel region is 0.1mm.It is set according to specifically mold is carried out without the requirement of fuel region size
Meter, the die forming under the pressure of 20MPa.
Step 5: by fuel region biscuit and without fuel region compound suppressing at IMDP biscuit.Mold is designed according to specific size,
The die forming under the pressure of 60MPa.
Step 6: carrying out pressureless sintering in a vacuum furnace.600 DEG C are warming up to the rate of 5/min first and keep the temperature 0.5h,
Carry out ungrease treatment, vacuum degree 10-2Pa.Argon gas protection, pressure 50kPa are passed to later.It is warming up to the rate of 10 DEG C/min
1700 DEG C, 1h is kept the temperature, furnace is cold.
Step 7: being required according to pellet size, grind off extra no fuel region, obtain the pellet fuel of final size.
Embodiment 2:
Step: 1: each powder: SiC is weighed in following specification and ratio, 50 μm, 96wt.%;Y2O3, 20 μm, 1wt.%;
Al2O3, 30 μm, 1wt.%;SiO2, 10nm, 1wt.%;Polyethyleneimine, molecular weight 1800,1wt.%.By above-mentioned powder and two
The mixing of times quality alcohol, is placed in nylon ball grinder, and mill ball uses alumina balls, ratio of grinding media to material 3:1, and ball milling obtains SiC slurry for 24 hours
Material.By the slurry equal part, portion is for coating TRISO particle;Another is dried for 24 hours at 80 DEG C, and SiC mixed powder is obtained after sieving
End.
Step 2: SiC mixed slurry is coated on TRISO particle by spray deposition.TRISO particle is placed on
It is rolled on vibrator, and imposes 100 DEG C of temperature.Using the SiC slurry prepared in step 1, mist is formed by spray generator
SiC powder is deposited on TRISO particle surface by shape slurry.Angle, size of dehiscing, spraying pressure by adjusting spray generator
The parameters such as power, flow velocity modulate suitable atomizing effect.By coating the SiC mixed-powder of different quality, can be obtained different
TRISO volume fraction.
Step 3: the TRISO particle die forming of SiC will have been coated, obtained fuel region biscuit.It is wanted according to fuel region size
Ask carry out mold design, and the die forming under the pressure of 60MPa.
Step 4: by SiC mixed-powder die forming, obtaining no fuel region biscuit.No fuel region biscuit include upper and lower covers and
Cyclic annular cylinder, with a thickness of 4mm, the fit clearance with fuel region is 0.25mm.According to specifically without fuel region size requirement progress mold
Design, the die forming under the pressure of 60MPa.
Step 5: by fuel region biscuit and without fuel region compound suppressing at IMDP biscuit.Mold is designed according to specific size,
The die forming under the pressure of 80MPa.
Step 6: carrying out pressureless sintering in a vacuum furnace.600 DEG C are warming up to the rate of 10 DEG C/min first and keep the temperature 2h,
Carry out ungrease treatment, vacuum degree 10Pa.Argon gas protection, pressure 10kPa are passed to later.1900 are warming up to the rate of 2 DEG C/min
DEG C, 5h is kept the temperature, furnace is cold.
Step 7: being required according to pellet size, grind off extra no fuel region, obtain the pellet fuel of final size.
Embodiment 3:
Step: 1: each powder: SiC is weighed in following specification and ratio, 50 μm, 87.5wt.%;Y2O3, 20 μm, 2wt.%;
Al2O3, 30 μm, 2wt.%;SiO2, 50 μm, 8wt.%;Polyethyleneimine, molecular weight 1800,0.5wt.%.By above-mentioned powder with
1.5 times of quality alcohol mixing, are placed in nylon ball grinder, and mill ball uses alumina balls, ratio of grinding media to material 3:1, and ball milling obtains for 24 hours
SiC slurry.By the slurry equal part, portion is for coating TRISO particle;Another is dried for 24 hours at 80 DEG C, and SiC is obtained after sieving
Mixed-powder.
Step 2: SiC mixed slurry is coated on TRISO particle by spray deposition.TRISO particle is placed on
It is rolled on vibrator, and imposes 85 DEG C of temperature.Using the SiC slurry prepared in step 1, mist is formed by spray generator
SiC powder is deposited on TRISO particle surface by shape slurry.Angle, size of dehiscing, spraying pressure by adjusting spray generator
The parameters such as power, flow velocity modulate suitable atomizing effect.By coating the SiC mixed-powder of different quality, can be obtained different
TRISO volume fraction.
Step 3: the TRISO particle die forming of SiC will have been coated, obtained fuel region biscuit.It is wanted according to fuel region size
Ask carry out mold design, and the die forming under the pressure of 25MPa.
Step 4: by SiC mixed-powder die forming, obtaining no fuel region biscuit.No fuel region biscuit include upper and lower covers and
Cyclic annular cylinder, with a thickness of 2mm, the fit clearance with fuel region is 0.1mm.It is set according to specifically mold is carried out without the requirement of fuel region size
Meter, the die forming under the pressure of 25MPa.
Step 5: by fuel region biscuit and without fuel region compound suppressing at IMDP biscuit.Mold is designed according to specific size,
The die forming under the pressure of 40MPa.
Step 6: carrying out pressureless sintering in a vacuum furnace.600 DEG C are warming up to the rate of 8/min first and keep the temperature 1h, into
Row ungrease treatment, vacuum degree 5 × 10-2Pa.Argon gas protection, pressure 30kPa are passed to later.It is warming up to the rate of 5 DEG C/min
1800 DEG C, 3h is kept the temperature, furnace is cold.
Step 7: being required according to pellet size, grind off extra no fuel region, obtain the pellet fuel of final size.
Embodiment 4:
Step: 1: each powder: SiC is weighed in following specification and ratio, 5 μm, 90wt.%;Y2O3, 5 μm, 3wt.%;
Al2O3, 10 μm, 5wt.%;SiO2, 5 μm, 1.5wt.%;Polyethyleneimine, molecular weight 1800,0.5wt.%.By above-mentioned powder
It mixes, is placed in nylon ball grinder with 1.8 times of quality alcohol, mill ball uses alumina balls, ratio of grinding media to material 3:1, and ball milling obtains for 24 hours
SiC slurry.By the slurry equal part, portion is for coating TRISO particle;Another is dried for 24 hours at 80 DEG C, and SiC is obtained after sieving
Mixed-powder.
Step 2: SiC mixed slurry is coated on TRISO particle by spray deposition.TRISO particle is placed on
It is rolled on vibrator, and imposes 90 DEG C of temperature.Using the SiC slurry prepared in step 1, mist is formed by spray generator
SiC powder is deposited on TRISO particle surface by shape slurry.Angle, size of dehiscing, spraying pressure by adjusting spray generator
The parameters such as power, flow velocity modulate suitable atomizing effect.By coating the SiC mixed-powder of different quality, can be obtained different
TRISO volume fraction.
Step 3: the TRISO particle die forming of SiC will have been coated, obtained fuel region biscuit.It is wanted according to fuel region size
Ask carry out mold design, and the die forming under the pressure of 30MPa.
Step 4: by SiC mixed-powder die forming, obtaining no fuel region biscuit.No fuel region biscuit include upper and lower covers and
Cyclic annular cylinder, with a thickness of 3mm, the fit clearance with fuel region is 0.15mm.According to specifically without fuel region size requirement progress mold
Design, the die forming under the pressure of 30MPa.
Step 5: by fuel region biscuit and without fuel region compound suppressing at IMDP biscuit.Mold is designed according to specific size,
The die forming under the pressure of 50MPa.
Step 6: carrying out pressureless sintering in a vacuum furnace.600 DEG C are warming up to the rate of 8/min first and keep the temperature 1.5h,
Carry out ungrease treatment, vacuum degree 5Pa.Argon gas protection, pressure 20kPa are passed to later.1850 are warming up to the rate of 5 DEG C/min
DEG C, 2h is kept the temperature, furnace is cold.
Step 7: being required according to pellet size, grind off extra no fuel region, obtain the pellet fuel of final size.
IMDP of the present invention is with anti-radiation performance is excellent, fission gas inclusiveness is good, thermal conductivity is high, security performance is excellent
Feature, preparation method science, process flow are simple, IMDP are prepared using the method for pressureless sintering, while realizing densification
Greatly improve preparation and production efficiency, it can be achieved that industrial mass production purpose, have substantive distinguishing features outstanding and aobvious
Write progress.
Above-described embodiment is only one of the preferred embodiment of the present invention, should not be taken to limit protection model of the invention
It encloses, as long as that in body design thought of the invention and mentally makes has no the change of essential meaning or polishing, is solved
The technical issues of it is still consistent with the present invention, should all be included within protection scope of the present invention.