CN105642907B - A kind of UO2W cermet ball preparation methods - Google Patents
A kind of UO2W cermet ball preparation methods Download PDFInfo
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- CN105642907B CN105642907B CN201610062445.1A CN201610062445A CN105642907B CN 105642907 B CN105642907 B CN 105642907B CN 201610062445 A CN201610062445 A CN 201610062445A CN 105642907 B CN105642907 B CN 105642907B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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Abstract
The invention discloses a kind of cermet level UO2The preparation method of W balls, the method includes the preparation of tungstenic colloidal sol, dispersion gelling, washing, drying and calcining, reduction sintering, annealing.The cermet level UO that the method is prepared2W bulb diameters are 0.05 ~ 3mm, and tungsten is evenly distributed on UO2Crystal boundary, compared with cermet level W UO prepared by powder method2Fuel has more preferable heat conductivity.
Description
Technical field
The present invention relates to Material Field, in particular it relates to a kind of UO2- W cermet ball preparation methods.
Background technology
UO2It is widely used in nuclear material, but pyroconductivity in metallic uranium, uranium carbide is minimum in uranium nitride.Heat transfer
Rate is an important thermophysical property in nuclear reactor, directly reflects the performance of reactor fuel.By preparing UO2- W gold
Category ceramic fuel can be such that reactor fuel runs at relatively low temperatures, reduce fuel temperature, reduce fuel core
Swelling, the diffusion that slow down core fission product, the release for decreasing fission product, it might even be possible to reduce uranium enrichment, plus
The burnup of deep reactor, economy is improve, extend the reactor operation life-span.
On UO2The report of-W cermet nuclear fuels is little, document《Literature review of thermal
and radiation performance parameters for high-temperature, uranium dioxide
fueled cermet materials》Describe UO2Powder disperse is in metal tungsten basal body using a fixed mold compacting sintering
The cermet W-UO of preparation2Fuel, document《A fabrication technique for a UO2 pellet
consisting of UO2grains and a continuous W channel on the grain boundary》In
Describe by ADU-UO2Powder mix with tungsten powder be pressed into pellet green compact it is sintered, annealing and be obtained tungsten in UO2Crystal boundary
The UO of continuous uniform distribution2- W ceramic pellets, under same pyroconductivity, UO2- W fuel ratios W-UO2The metal W of fuel addition
Less, it is more beneficial for UO2Fuel kernel performance；Both approaches are all to prepare cermet W-UO by powder method2And UO2- W fires
Material.And the fuel tungsten therein that powder method is prepared is in UO2Distribution in crystal boundary is simultaneously uneven so that metal UO2- W's
Pyroconductivity is not high.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of UO2It is prepared by-W cermet ball preparation methods, the method
UO2- W cermets ball and cermet W-UO2Pellet and UO2- W pellet preparation technologies are very different, and preparation technology difficulty is big
（For example how to prepare complete indehiscent ball, how to allow tungsten to be evenly distributed on UO2In crystal boundary）, the metal prepared
Ceramic grade UO2- W bulb diameters are 0.05~3mm, and tungsten is evenly distributed on UO2Crystal boundary, this cermet level UO2- W balls are not
Can ftracture, pyroconductivity is high.
The present invention the used technical scheme that solves the above problems is：
A kind of cermet level UO2The preparation method of-W balls, it is comprised the following steps that：
The preparation of step 1 tungstenic colloidal sol：It is 0.10~0.156, urea/U according to ammonium metatungstate/U mass ratioes at 5 DEG C
Mol ratio is 1：4 ratios mix ammonium metatungstate, scarce uranyl nitrate solution and urea, stir, then according to HTMA（Wu Luo
Tropine）The mol ratio of/U is 1：4 ratio, solid HTMA is slowly added in the case where being stirred continuously（Methenamine）, stirring
It is uniform transparent to tungstenic sol solutionses.
Step 2 dispersion gelling：By tungstenic sol solutionses by pressure venting, colloidal sol drop is obtained.Colloidal sol drop is carried through carrier band stream
Band, instills the isooctanol equipped with heating（Or paraffin oil, carbon tetrachloride CCl4）The balling-up under surface tension effects in dispersion column, and
It is gelled during decline, obtains tungstenic gel ball.To ensure enough gelling times, dispersion column length is not less than 2m, disperses
Medium is isooctanol（Or paraffin oil, CCl4）65 ~ 80 DEG C should be maintained.
Step 3 is washed：Tungstenic gel ball is washed with ethanol water, ethanol washing lotion concentration is 40% ~ 60%（Volume
Than）, scavenging period is 0.5 ~ 1h, is washed three times.
Step 4 drying and calcining：Tungstenic gel ball is put into follow procedure in high temperature oven to heat up, calcining, gel is dried
Ball completes dehydration and organic matter skeleton subtractive process, and is converted into UO3-WO3Ball.Temperature-programmed mode is room temperature to 80 DEG C of intensifications
Time 60min ~ 120min；80 DEG C ~ 150 DEG C heating-up time 120min ~ 150min；150 DEG C ~ 200 DEG C heating-up time 90min ~
120min；200 DEG C are warming up to 350 DEG C of heating-up times for 120min ~ 150min.
Step 5 reduction sintering：By WO3-UO3Ball is at 1300~1400 DEG C of atmosphere of hydrogen in sintering furnace through reduction sintering 40
~60min, WO3-UO3Ball is reduced into cermet level W-UO2Ball.In fact, sintering time in 40~60min all can,
60min is optimal.
Step 6 is annealed：By cermet level W-UO2Ball CO in sintering furnace2Atmosphere（1550~1600）20 at DEG C
~30min, cermet level W-UO2The tungsten of ball is by CO2Gas is oxidized to WO3, and liquefy into ceramic grade UO2Intergranular（WO3
Fusing point is 1470 DEG C）, obtain UO2-WO3Ball.
Step 7 is reduced：By the UO after the obtained liquefaction of step 62-WO3Ball is in 1500~1600 DEG C of sintering furnace atmosphere of hydrogen
It is lower to sinter 100~120min through reduction, obtain tungsten and be evenly distributed on ceramic UO2The cermet level UO of crystal boundary2- W balls.
Key point of the invention is how tungsten to be dispersed in into UO2In, the present invention is by by preparation process
Technique is strictly controlled, and such as sintering temperature is no more than 1400 DEG C, and sintering time is different in preparation process no more than 60min
Switching of atmosphere etc., ensure that tungsten can be dispersed in UO2In, while being prepared into the UO for coming2- W cermet balls
Will not be excessively fine and close because of sintering, it is ensured that UO2- W cermets ball will not ftracture.
To sum up, the beneficial effects of the invention are as follows：
The present invention passes through the preparation of tungstenic colloidal sol, disperses gelling, washing, drying and calcining, reduction sinter, anneal, reducing
Arrive tungsten and be evenly distributed on ceramic UO2The cermet level UO of crystal boundary2- W balls, cermet level obtained in this method
UO2Tungsten in-W balls is evenly distributed in ceramic UO2Crystal boundary, has more preferable than cermet material obtained in powder method
Heat conductivity.
Brief description of the drawings
Fig. 1 is evenly distributed on UO for W2Metallograph between crystal.
Specific embodiment
With reference to embodiment and accompanying drawing, detailed description further, but embodiments of the present invention are made to the present invention
Not limited to this.
Embodiment 1：
A kind of cermet level UO2The preparation method of-W balls, specifically includes following steps：
The preparation of step 1 tungstenic colloidal sol：At 5 DEG C, in 20ml acid deficient uranyl nitrate solutions（[U]=500g/L）In, add
Plus 35.3g urea and 1.0g ammonium metatungstates, it is completely dissolved by stirring to solid, then slowly add in the case where being stirred continuously
Plus HTMA（Methenamine）82.3g, until tungstenic sol solutionses are transparent.
Step 2 dispersion gelling：By tungstenic sol solutionses with 0.07~0.1Mpa pressure ventings, colloidal sol is by a diameter of
The orifice plate dispersion of 0.2mm, 0.3mm, orifice plate vibrates and obtains colloidal sol drop.Colloidal sol flows through dispersion orifice plate passage and should be maintained at 5 DEG C
Below.Colloidal sol drop is instilled in isooctanol dispersion column or paraffin oil dispersion column equipped with heating through carrier band stream carrier band, and colloidal sol drops in table
Balling-up under the tension force effect of face, and be gelled during decline, obtain tungstenic gel ball.To ensure enough gelling times, dispersion
Column length is not less than 2m, and decentralized medium is isooctanol（Or paraffin oil）70 ~ 80 DEG C should be maintained.
Step 3 is washed：Tungstenic gel ball is washed with ethanol water, ethanol washing lotion concentration is 40% ~ 60%（Volume
Than）, scavenging period is 0.5 ~ 1h, is washed three times.
Step 4 drying and calcining：Tungstenic gel ball is put into high temperature oven and is dried calcining, gel ball completes dehydration
With organic matter skeleton subtractive process, and UO is converted into3-WO3Ball.Temperature-programmed mode be room temperature to 80 DEG C of heating-up time 60min ~
120min；80 DEG C ~ 150 DEG C heating-up time 120min ~ 150min；150 DEG C ~ 200 DEG C heating-up time 90min ~ 120min；200℃
350 DEG C of heating-up times are warming up to for 120min ~ 150min.
Step 5 reduction sintering：By WO3-UO3Ball is at 1300~1400 DEG C of atmosphere of hydrogen in sintering furnace through reduction sintering 40
~60min, WO3-UO3Ball is reduced into cermet level W-UO2Ball.
Step 6 is annealed：By cermet level W-UO2Ball CO in sintering furnace2Atmosphere（1550~1600）20 at DEG C
~30min, cermet level W-UO2The tungsten of ball is by CO2Gas is oxidized to WO3, and liquefy into ceramic grade UO2Intergranular（WO3
Fusing point is 1470 DEG C）, obtain UO2-WO3Ball.
Step 7 is reduced：By the UO after the obtained liquefaction of step 62-WO3Ball is in 1500~1600 DEG C of sintering furnace atmosphere of hydrogen
Lower to sinter 100~120min through reduction, the tungsten for obtaining a diameter of 0.05~0.5mm is evenly distributed on ceramic UO2Crystal boundary
Cermet level UO2It is 6.1% that -6.1m%W balls, wherein W account for cermet ball mass fraction.
Embodiment 2
Step 1 addition ammonium metatungstate is 1.56g, and remaining is with implementation 1；
Step 2 dispersion gelling：It is the dispersion of 2mm, 4mm, 6mm by dispersion aperture that tungstenic sol solutionses are used into peristaltic pump
Head obtains the colloidal sol drop of certain size.Colloidal sol flows through dispersion orifice plate passage and should be maintained at less than 5 DEG C.Colloidal sol drop is carried through carrier band stream
Band, instills the CCl equipped with heating4The balling-up under surface tension effects in dispersion column, and be gelled during decline, obtain tungstenic
Gel ball.To ensure enough gelling times, dispersion column length is not less than 2m, and decentralized medium is CCl4, 65 ~ 75 should be maintained
℃；
Step 3 is with implementation 1；
Step 4 is with implementation 1；
Step 5 is with implementation 1；
Step 6 is with implementation 1；
Step 7 is evenly distributed on ceramic UO with 1 tungsten for obtaining a diameter of 0.6~3mm is implemented2The metal pottery of crystal boundary
Porcelain level UO2- 9.4m%W balls such as Fig. 1, it is 9.4% that wherein W accounts for cermet ball mass fraction.
The cermet level UO that the present invention is prepared2The pyroconductivity of-W balls and other balls is more as shown in table 1：
As can be seen from the above table, the cermet level UO for being prepared through the present invention2The pyroconductivity of-W balls is apparently higher than powder
Method prepares cermet W-UO2Fuel.
As described above, the present invention can be realized preferably.
Claims (7)
1. a kind of UO2- W cermet ball preparation methods, it is characterised in that comprise the following steps that：
The preparation of step 1, tungstenic colloidal sol：It is 0.10~0.156, urea/U moles according to ammonium metatungstate/U mass ratioes at 5 DEG C
Than being 1：4 ratio mixes ammonium metatungstate, scarce uranyl nitrate solution and urea, stirs, then according to methenamine/U
Mol ratio be 1：4 ratio, solid methenamine is slowly added in the case where being stirred continuously, and is evenly stirred until tungstenic colloidal sol
Liquid is transparent；
Step 2, dispersion gelling：By the tungstenic sol solutionses described in step 1 by pressure venting, colloidal sol drop is obtained, colloidal sol drop is through carrying
Band stream is carried, and is instilled in any one dispersion column of isooctanol, paraffin oil or carbon tetrachloride equipped with heating, colloidal sol is dropped in surface
Balling-up under tension force effect, and be gelled during decline, obtain tungstenic gel ball；
Step 3, washing：Tungstenic gel ball is washed with ethanol water；
Step 4, drying and calcining：Tungstenic gel ball is put into high temperature oven and is dried calcining to be dehydrated and remove organic matter bone
Frame takes off, and is finally translated into UO3-WO3Ball；
Step 5, for the first time reduction sintering：By WO3-UO3Reduction sintering obtains cermet level W-UO2Ball；
Step 6, annealing：Cermet level W-UO2The tungsten of ball is by CO2Gas is oxidized to WO3, and liquefy into ceramic grade UO2
Intergranular, obtains UO2-WO3Ball；
Step 7, second reduction sintering：By the UO after the obtained liquefaction of step 62-WO3Ball reduction sintering obtains cermet level
UO2- W balls.
2. UO according to claim 12- W cermet ball preparation methods, it is characterised in that the dispersion column length in step 2
Degree is not less than 2m, and decentralized medium is isooctanol, paraffin oil or CCl4Temperature at 65 ~ 80 DEG C.
3. UO according to claim 12- W cermet ball preparation methods, it is characterised in that the ethanol of step 3 washing
Washing lotion concentration volume ratio is 40% ~ 60%, and scavenging period is 0.5 ~ 1h, is washed three times.
4. UO according to claim 12- W cermet ball preparation methods, it is characterised in that the drying and calcining mistake of step 4
Cheng Wei：Room temperature is to 80 DEG C of heating-up time 60min ~ 120min, 80 DEG C ~ 150 DEG C heating-up time 120min ~ 150min, 150 DEG C ~ 200
DEG C heating-up time 90min ~ 120min, 200 DEG C are warming up to 350 DEG C of heating-up times for 120min ~ 150min.
5. the UO according to claim any one of 1-42- W cermet ball preparation methods, it is characterised in that step 5 also
The condition of original sintering is specially：40~60min of sintering is reduced at 1300~1400 DEG C of atmosphere of hydrogen.
6. UO according to claim 52- W cermet ball preparation methods, it is characterised in that step 6 is in CO2Atmosphere
Under, by cermet level W-UO2In ball input sintering furnace, 20~30min is kept at 1550~1600 DEG C.
7. UO according to claim 62- W cermet ball preparation methods, it is characterised in that the reduction sintering of step 7
Condition is specially：Through 100~120min of reduction sintering at 1500~1600 DEG C of atmosphere of hydrogen.
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| CN107256726B (en) * | 2017-07-03 | 2019-04-30 | 中国工程物理研究院材料研究所 | A kind of preparation method of metal reinforced uranium dioxide fuel ball |
| CN115722664A (en) * | 2022-12-02 | 2023-03-03 | 中国核动力研究设计院 | Composite material with uniform framework structure and preparation method and application thereof |
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| US3759787A (en) * | 1960-09-30 | 1973-09-18 | Nasa | Nuclear fuel elements |
| US3429699A (en) * | 1967-07-24 | 1969-02-25 | Atomic Energy Commission | High loaded uo2-columbium cermets |
| JPS6173803A (en) * | 1984-09-17 | 1986-04-16 | Mitsubishi Nuclear Fuel Co Ltd | Production of powder mixture composed of uranium dioxide and gadolinium oxide for producing nuclear fuel pellet |
| CN1029578C (en) * | 1990-11-30 | 1995-08-23 | 清华大学 | Nuclear fuel micro ball prepared by full gelatinizing method |
| CN100427427C (en) * | 2006-12-15 | 2008-10-22 | 清华大学 | Method of preparing UO2 ceramic fuel microsphere |
| CN100551832C (en) * | 2007-10-12 | 2009-10-21 | 清华大学 | A kind of preparation high temperature nuclear reactor fuel element UO 2The method of nuclear core |
| CN104446479A (en) * | 2014-11-06 | 2015-03-25 | 中国核动力研究设计院 | Method of preparing ceramic grade uranium dioxide ball |
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