Summary of the invention
The present invention is quasi- to pass through preparation nanometer UO2Material and its composite material fuel pellet, to improve the heat of fuel pellet
Physical property, mechanical property and fission gas carrying capacity, to promote the safety of reactor.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of the fuel pellet based on nanometer titanium dioxide uranium or its compound, which is characterized in that including with
Lower step,
Step 1: nanometer titanium dioxide uranium or its composite powder are placed in nylon ball grinder, add the wine of 1-2 times of quality
The zirconium oxide abrasive ball of essence and 3 times of quality, wet mixing for 24 hours, dry under the conditions of 70-100 DEG C later, obtain ovendry power;
Step 2: ovendry power is subjected to pressureless sintering, hot pressed sintering, discharge plasma sintering or flash burning, heat-insulation pressure keeping knot
Furnace cooling after beam, machine-shaping to get arrive fuel pellet.
Specifically, in the step 2, when ovendry power is into when pressureless sintering, the steps include: ovendry power in 100-
It is pressed and molded under the conditions of 400Mpa, obtains fuel pellet biscuit, then fuel pellet biscuit is placed in hydrogen or other atmosphere protections
Under atmosphere sintering furnace in, pressure be 10-50Mpa under the conditions of, 600 DEG C of left sides are warming up to the rate of 5~10 DEG C/min first
Right and 0.5~2h of heat preservation, then it is warming up to 1300-1800 DEG C with the rate of 1-10 DEG C/min, keep the temperature 1-5h.
Specifically, in the step 2, when ovendry power is into hot pressed sintering, the steps include: ovendry power being placed in graphite
In mold, it is evacuated to 5 × 10 in a hydrogen atmosphere-2-5×10-1Pa, under the conditions of the sintering pressure of 20-100MPa, with 1-
The rate of 20 DEG C/min is warming up to 1300-1800 DEG C and keeps the temperature 1-4h.
Specifically, in the step 2, when ovendry power is sintered into discharge plasma, the steps include: ovendry power
It is placed in graphite jig, is evacuated to 5 × 10-2-5×10-1Pa, later applying argon gas to 10-60kPa;In the burning of 20-100MPa
Under the conditions of knot pressure power, it is warming up to 1200-1800 DEG C with the rate of 50-1000 DEG C/min, and keep the temperature 1-30min.
More specifically, in the step 2, when ovendry power is into flash burning, the steps include: for ovendry power to be placed in graphite or
In metal die, it is evacuated to 5 × 10-2-5×10-1Pa, later applying argon gas to 10-60kPa;With the speed of 400-2000 DEG C/min
Rate is warming up to 1200-1800 DEG C, and keeps the temperature 20s-5min.
Further, the preparation method of the nanometer titanium dioxide uranium includes hydro-thermal method and the precipitation method;
The hydro-thermal method obtains mixing molten the following steps are included: precursor and reducing agent are dissolved in deionized water respectively
Liquid A, the concentration of presoma is 0.01-0.5mol/L in mixed solution A, and the concentration of reducing agent is 0.01-0.5mol/L;It will mixing
Solution A is transferred in hydrothermal reaction kettle, reacts 4-24h under the conditions of 160-240 DEG C;After cooling, obtained sediment is centrifuged
Separation, and rinsed using alcohol and deionized water, finally nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C;Its
In, the presoma is uranium acetate or uranyl nitrate;The reducing agent is ethylenediamine or tripropyl amine (TPA).
The precipitation method obtain mixing molten the following steps are included: precursor and precipitating reagent are dissolved in deionized water respectively
The concentration of presoma is 0.01-0.5mol/L in liquid B, mixed solution B, and the concentration of reducing agent is 0.001-0.5mol/L;Stirring
After uniformly, 0.1-12h is reacted under the conditions of 60-100 DEG C;After cooling, obtained sediment is centrifugated, and using alcohol and
Deionized water is rinsed, and finally nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C;Wherein, the presoma is vinegar
Sour uranyl or uranyl nitrate;The precipitating reagent is hexa, urea or graphene.
Preferably, the partial size of the nanometer titanium dioxide uranium is 10nm-500nm,235U degree of enrichment is 1-5%.
Further, the preparation method of the nanometer titanium dioxide uranium compound includes hydro-thermal method and the precipitation method;
The hydro-thermal method obtains the following steps are included: precursor, reducing agent and additive are dissolved in deionized water respectively
Mixed solution C, the concentration of presoma is 0.01-0.5mol/L in mixed solution C, and the concentration of reducing agent is 0.01-0.5mol/L,
The additive amount of additive is the 1%-10%vol of nanometer titanium dioxide uranium theoretical yield;Mixed solution C is transferred to hydrothermal reaction kettle
In, 4-24h is reacted under the conditions of 160-240 DEG C;After cooling, by obtained sediment be centrifugated, and using alcohol and go from
Sub- water rinses, and finally nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C;Wherein, the presoma is acetic acid uranium
Acyl or uranyl nitrate;The reducing agent is ethylenediamine, tripropyl amine (TPA) or hydrazine hydrate;
The precipitation method obtain the following steps are included: precursor, precipitating reagent and additive are dissolved in deionized water respectively
The concentration of presoma is 0.01-0.5mol/L in mixed solution D, mixed solution D, and the concentration of reducing agent is 0.001-0.5mol/
L, the additive amount of additive are the 0%-10%vol of nanometer titanium dioxide uranium theoretical yield;After mixing evenly, in 60-100 DEG C of condition
Lower reaction 0.1-12h;After cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C;Wherein, the presoma is uranium acetate or uranyl nitrate;Institute
Stating precipitating reagent is that hexa, urea or hydrazine hydrate add graphene.
Preferably, the partial size of the nanometer titanium dioxide uranium compound is 10nm-15 μm,235U degree of enrichment is 1-5%.
Preferably, the additive is any one or more following combination: the SiC particulate that partial size is 20nm-2 μm,
The SiC whisker that diameter is 20nm-200nm, length is 5-20 μm, the carbon nanometer that diameter 5nm-100nm, length are 1-20 μm
Pipe, the graphene that plane length is 100nm-200 μm, the Nano diamond that partial size is 20nm-10 μm.
Compared with prior art, the invention has the following advantages:
The nano combined fuel pellet being prepared enriches defect as caused by nanoscale particle and cavity can be more
The generation of good inhibition irradiation damage, and can preferably accommodate fission gas ability.Therefore the method for the present invention is prepared
Fuel pellet has the characteristics that high-melting-point, high thermal conductivity, anti-radiation performance are good, fission gas carrying capacity is strong, excellent in mechanical performance,
It can be used as the novel nuclear fuel of nuclear power station.
Specific embodiment
Below with reference to embodiment, the invention will be further described, and mode of the invention includes but are not limited to following implementation
Example.
Firstly, providing the preparation side of the present embodiment raw material nano uranium dioxide and its compound below with example 1-12
Method, secondly, providing the method for preparing fuel pellet using above-mentioned raw materials again with example 13-20.
Specifically, the method that elder generation example 1-3 prepares nanometer titanium dioxide uranium for the present embodiment with hydro-thermal method below, specifically such as
Under:
Example 1
Step 1: uranium acetate and ethylenediamine are dissolved in deionized water respectively, obtain mixed solution, is made in mixed solution
The concentration of uranium acetate is 0.01mol/L, and the concentration of ethylenediamine is 0.01mol/L;Mixed solution is transferred to hydrothermal reaction kettle
In, 4h is reacted under the conditions of 160 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 2
Step 1: uranyl nitrate and tripropyl amine (TPA) are dissolved in deionized water respectively, obtain mixed solution, is made in mixed solution
The concentration of uranium acetate is 0.5mol/L, and the concentration of tripropyl amine (TPA) is 0.5mol/L;Mixed solution is transferred in hydrothermal reaction kettle,
It is reacted for 24 hours under the conditions of 240 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 3
Step 1: uranium acetate and hydrazine hydrate are dissolved in deionized water respectively, obtain mixed solution, is made in mixed solution
The concentration of uranium acetate is 0.2mol/L, and the concentration of hydrazine hydrate is 0.05mol/L;Mixed solution is transferred to hydrothermal reaction kettle
In, 18h is reacted under the conditions of 200 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Following example 4-6 is the method that the present embodiment prepares nanometer titanium dioxide uranium with the precipitation method, specific as follows:
Example 4
Step 1: uranium acetate and hexa are dissolved in deionized water respectively, obtain mixed solution, are mixed molten
The concentration of uranium acetate is 0.01mol/L in liquid, and the concentration of hexa is 0.001mol/L;After mixing evenly, 60
0.1h is reacted under the conditions of DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 5
Step 1: uranyl nitrate and urea are dissolved in deionized water respectively, obtain mixed solution, nitric acid in mixed solution
The concentration of uranyl is 0.5mol/L, and the concentration of urea is 0.5mol/L;After mixing evenly, 12h is reacted under the conditions of 100 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 6
Step 1: uranium acetate and hydrazine hydrate, graphene are dissolved in deionized water respectively, obtain mixed solution B, mixing
The concentration of presoma is 0.5mol/L in solution B, and the concentration of hydrazine hydrate is 0.01mol/L, and graphene concentration is 0.05g/L;It stirs
After mixing uniformly, 8h is reacted under the conditions of 80 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
The nanometer titanium dioxide uranium material that examples detailed above 1-6 is prepared, after measured,235U degree of enrichment is 1-5%, sieving
The powder that partial size is 10nm-500nm is chosen afterwards prepares fuel pellet as raw material nanometer titanium dioxide uranium.
Following example 7-9 is the method that the present embodiment prepares nanometer titanium dioxide uranium composite powder with hydro-thermal method, specifically
It is as follows:
Example 7
Step 1: uranium acetate and ethylenediamine are dissolved in deionized water respectively, obtain mixed solution, is made in mixed solution
The concentration of uranium acetate is 0.01mol/L, and the concentration of ethylenediamine is 0.01mol/L, then addition nanometer titanium dioxide uranium reason thereto
By the SiC particulate of the 1%vol of yield, the partial size of SiC particulate is 20nm-2 μm;Then it is anti-mixed solution to be transferred to hydro-thermal again
It answers in kettle, reacts 4h under the conditions of 160 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 8
Step 1: uranyl nitrate and tripropyl amine (TPA) are dissolved in deionized water respectively, obtain mixed solution, is made in mixed solution
The concentration of uranium acetate is 0.5mol/L, and the concentration of tripropyl amine (TPA) is 0.5mol/L, then addition nanometer titanium dioxide uranium is theoretical thereto
The SiC whisker of the 5%vol of yield, the diameter of SiC whisker is 20nm-200nm, length is 5-20 μm;Mixed solution is transferred to
In hydrothermal reaction kettle, reacted for 24 hours under the conditions of 240 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 9
Step 1: uranium acetate and hydrazine hydrate are dissolved in deionized water respectively, obtain mixed solution, is made in mixed solution
The concentration of uranium acetate is 0.2mol/L, and the concentration of hydrazine hydrate is 0.05mol/L, then addition nanometer titanium dioxide uranium is theoretical thereto
The carbon nanotube of the 10%vol of yield, the diameter of carbon nanotube is 5nm-100nm, length is 1-20 μm;Mixed solution is shifted
Into hydrothermal reaction kettle, 18h is reacted under the conditions of 200 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Following example 10-12 is the method that the present embodiment prepares nanometer titanium dioxide uranium composite powder with the precipitation method, tool
Body is as follows:
Example 10
Step 1: uranium acetate and hexa are dissolved in deionized water respectively, obtain mixed solution, are mixed molten
The concentration of uranium acetate is 0.01mol/L in liquid, and the concentration of hexa is 0.001mol/L, then adds nanometer thereto
The SiC particulate of the 1%vol of uranium dioxide theoretical yield, the partial size of SiC particulate are 20nm-2 μm;After mixing evenly, in 60 DEG C of items
0.1h is reacted under part;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 11
Step 1: uranyl nitrate and urea are dissolved in deionized water respectively, obtain mixed solution, nitric acid in mixed solution
The concentration of uranyl is 0.5mol/L, and the concentration of urea is 0.5mol/L, then adds nanometer titanium dioxide uranium theoretical yield thereto
The graphene of 5%vol, the plane length of graphene are 100nm-200 μm;After mixing evenly, 12h is reacted under the conditions of 100 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
Example 12
Step 1: uranium acetate and hydrazine hydrate, graphene are dissolved in deionized water respectively, obtain mixed solution B, mixing
The concentration of presoma is 0.5mol/L in solution B, and the concentration of hydrazine hydrate is 0.01mol/L, and graphene concentration is 0.01g/L, then
The Nano diamond of the 10%vol of nanometer titanium dioxide uranium theoretical yield is added thereto, and the partial size of Nano diamond is 20nm-10
μm;After mixing evenly, 8h is reacted under the conditions of 80 DEG C;
Step 2: after cooling, obtained sediment is centrifugated, and is rinsed using alcohol and deionized water, is finally existed
Nanometer titanium dioxide uranium can be obtained in drying under the conditions of 60-100 DEG C.
The nanometer titanium dioxide uranium composites that examples detailed above 7-12 is prepared, after measured,235U degree of enrichment is 1-
5%, the powder that partial size is 10nm-15 μm is chosen after sieving prepares fuel pellet as raw material nanometer titanium dioxide uranium.
The side that fuel pellet is prepared using above-mentioned nanometer titanium dioxide uranium as raw material is provided by taking example 13-16 as an example again below
Method, specific as follows:
Example 13
Nanometer titanium dioxide uranium powder is placed in nylon ball grinder by step 1, adds the alcohol and 3 times of matter of 1-2 times of quality
The zirconium oxide abrasive ball of amount, wet mixing for 24 hours, dry under the conditions of 70-100 DEG C later, obtain ovendry power;
Step 2 carries out sintering as follows:
By mixed-powder die forming, fuel pellet biscuit, forming pressure 400Mpa are obtained;
Biscuit is placed in atmosphere sintering furnace and carries out pressureless sintering, is warming up to 600 DEG C first with the rate of 5~10 DEG C/min
Control and keep the temperature 0.5h, vacuum degree 10-2- 10Pa is warming up to 1800 DEG C with the rate of 1 DEG C/min, keeps the temperature 5h, furnace is cold, and atmosphere is
Hydrogen shield, 10~50kPa of pressure.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
Example 14
Step 1 matches raw material as follows:
By nanometer UO2Powder is placed in nylon ball grinder, adds the alcohol of 1-2 times of quality and the zirconium oxide of 3 times of quality
Mill ball, wet mixing for 24 hours, are dried for 24 hours at 70-100 DEG C later.
Step 2 carries out sintering as follows:
Mixed-powder is placed in designed graphite jig, hot pressed sintering is carried out, sintering process is as follows: being evacuated to 5
×10-2-5×10-1Pa rises to 600 DEG C with the rate of 10 DEG C/min;1200 DEG C are warming up to the rate of 1 DEG C/min and are kept the temperature
5h, while applying the sintering pressure of 100MPa, furnace cooling after heat-insulation pressure keeping, sintering atmosphere is hydrogen.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
Example 15
Step 1 matches raw material as follows:
By nanometer UO2Powder is placed in nylon ball grinder, adds the alcohol of 1-2 times of quality and the zirconium oxide of 3 times of quality
Mill ball, wet mixing for 24 hours, are dried for 24 hours at 70-100 DEG C later.
Step 2 carries out sintering as follows:
By nanometer UO2Powder is placed in designed graphite jig, carries out discharge plasma sintering, and sintering process is as follows:
It is evacuated to 5 × 10-2-5×10-1Pa, later applying argon gas to 10-60kPa;1300 DEG C are warming up to 500 DEG C/min, and is applied
The sintering pressure of 50MPa keeps the temperature 5min, furnace cooling after heat-insulation pressure keeping.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
Example 16
Step 1 matches raw material as follows:
By nanometer UO2Powder is placed in nylon ball grinder, adds the alcohol of 1-2 times of quality and the zirconium oxide of 3 times of quality
Mill ball, wet mixing for 24 hours, are dried for 24 hours at 70-100 DEG C later.
Step 2 carries out sintering as follows:
By nanometer UO2Powder is placed in designed graphite or metal die, carries out flash burning sintering, and sintering process is as follows:
It is evacuated to 5 × 10-2-5×10-1Pa, later applying argon gas to 10-60kPa;1600 DEG C are warming up to 2000 DEG C/min, and is applied
The sintering pressure of 40MPa keeps the temperature 2min, furnace cooling after heat-insulation pressure keeping.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
The side that fuel pellet is prepared using above-mentioned nanometer titanium dioxide uranium as raw material is provided by taking example 17-20 as an example again below
Method, specific as follows:
Example 17
Step 1, by nanometer UO2/ SiC ceramic matrix composite material powder is placed in nylon ball grinder, adds 1-2 times of quality
The zirconium oxide abrasive ball of alcohol and 3 times of quality, wet mixing for 24 hours, dry under the conditions of 70-100 DEG C later, obtain ovendry power;
Step 2 carries out sintering as follows:
By mixed-powder die forming, fuel pellet biscuit, forming pressure 300Mpa are obtained;
Biscuit is placed in atmosphere sintering furnace and carries out pressureless sintering, 600 DEG C of left sides are warming up to the rate of 10 DEG C/min first
The right side simultaneously keeps the temperature 0.5h, vacuum degree 10-2- 10Pa is warming up to 1800 DEG C with the rate of 1 DEG C/min, keeps the temperature 5h, furnace is cold, and atmosphere is hydrogen
Gas shielded, 10~50kPa of pressure.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
Example 18
Step 1 matches raw material as follows:
By nanometer UO2/ carbon nano tube compound material powder is placed in nylon ball grinder, add 1-2 times of quality alcohol with
And the zirconium oxide abrasive ball of 3 times of quality, wet mixing for 24 hours, are dried for 24 hours at 70-100 DEG C later.
Step 2 carries out sintering as follows:
Mixed-powder is placed in designed graphite jig, hot pressed sintering is carried out, sintering process is as follows: being evacuated to 5
×10-2-5×10-1Pa rises to 600 DEG C with the rate of 10 DEG C/min;1200 DEG C are warming up to the rate of 1 DEG C/min and are kept the temperature
5h, while applying the sintering pressure of 100MPa, furnace cooling after heat-insulation pressure keeping, sintering atmosphere is hydrogen.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
Example 19
Step 1 matches raw material as follows:
By nanometer UO2/ graphene composite material powder is placed in nylon ball grinder, adds the alcohol and 3 of 1-2 times of quality
The zirconium oxide abrasive ball of times quality, wet mixing for 24 hours, later 70-100 DEG C of drying for 24 hours.
Step 2 carries out sintering as follows:
By nanometer UO2/ graphene composite material powder is placed in designed graphite jig, carries out plasma discharging burning
Knot, sintering process are as follows: being evacuated to 5 × 10-2-5×10-1Pa, later applying argon gas to 10-60kPa;With 500 DEG C/min heating
To 1300 DEG C, and apply the sintering pressure of 50MPa, keeps the temperature 5min, furnace cooling after heat-insulation pressure keeping.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
Example 20
Step 1 matches raw material as follows:
By nanometer UO2/ Nano diamond powder is placed in nylon ball grinder, adds the alcohol and 3 times of matter of 1-2 times of quality
The zirconium oxide abrasive ball of amount, wet mixing for 24 hours, are dried for 24 hours at 70-100 DEG C later.
Step 2 carries out sintering as follows:
By nanometer UO2/ Nano diamond powder is placed in designed graphite or metal die, carries out flash burning sintering, is burnt
Knot technique is as follows: being evacuated to 5 × 10-2-5×10-1Pa, later applying argon gas to 10-60kPa;It is warming up to 2000 DEG C/min
1600 DEG C, and apply the sintering pressure of 40MPa, keep the temperature 2min, furnace cooling after heat-insulation pressure keeping.
Step 3 takes out sample after furnace cooling, is machined to required geomery.
The step of of the invention its optimizes raw material nano uranium dioxide and its compound preparation process and parameter, and optimize
The step of fuel pellet preparation process and parameter make it using first preparation is also able to carry out with the installations and facilities of routine, have
Preparation method advantages of simple, feature easy to operate, also, after measured, the fuel pellet being prepared using the method for the present invention,
Have the characteristics that high-melting-point, high thermal conductivity, anti-radiation performance are good, fission gas carrying capacity is strong, excellent in mechanical performance, can be used as core
The novel nuclear fuel in power station.
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.