CN105642907A - UO2-W metal ceramic ball preparation method - Google Patents
UO2-W metal ceramic ball preparation method Download PDFInfo
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- CN105642907A CN105642907A CN201610062445.1A CN201610062445A CN105642907A CN 105642907 A CN105642907 A CN 105642907A CN 201610062445 A CN201610062445 A CN 201610062445A CN 105642907 A CN105642907 A CN 105642907A
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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 preparation method of metal ceramic UO2-W balls. The method comprises preparation of tungsten-contained sol, gel dispersion, washing, drying and calcining, reduction and sintering, and annealing. The metal ceramic UO2-W balls, prepared by the method, have diameters of 0.05-3 mm; metal tungsten is uniformly distributed at a UO2 grain boundary; and the metal ceramic UO2-W balls are better in heat conductivity compared with metal ceramic W-UO2 fuels prepared by a powder method.
Description
Technical field
The present invention relates to Material Field, in particular it relates to a kind of UO2-W ceramic metal ball preparation method.
Background technology
UO2It is widely used in nuclear material, but pyroconductivity is at metallic uranium, uranium carbide, uranium nitride is minimum. Pyroconductivity is an important thermophysical property in nuclear reactor, directly reflects the performance of reactor fuel. By preparing UO2-W cermet fuel can make reactor fuel run at relatively low temperatures, reduce fuel temperature, decrease fuel nuclear core swelling, slow down the diffusion of nuclear core fission product, decrease the release of fission product, even can reduce uranium enrichment, deepen the burnup of reactor, improve economy, extend the reactor operation life-span.
About UO2The report of-W ceramic metal nuclear fuel is little, and document " Literaturereviewofthermalandradiationperformanceparamete rsforhigh-temperature, uraniumdioxidefueledcermetmaterials " describes UO2Powder disperse adopts a fixed mold compacting sintering and the ceramic metal W-UO for preparing in tungsten matrix2Fuel, document " AfabricationtechniqueforaUO2pelletconsistingofUO2GrainsandacontinuousWchannelonthegrainboundary " in describe and pass through ADU-UO2Powder mix with tungsten powder be pressed into pellet green compact sintered, annealing and prepare tungsten at UO2The UO of crystal boundary continuous uniform distribution2-W ceramic pellet, under same pyroconductivity, UO2-W fuel ratio W-UO2The metal W that fuel adds is less, is more beneficial for UO2Fuel kernel performance; Both approaches is all prepare ceramic metal W-UO by powder method2And UO2-W fuel. And the fuel tungsten therein that powder method prepares is at UO2Distribution in crystal boundary is also uneven so that metal UO2The pyroconductivity of-W is not high.
Summary of the invention
The technical problem to be solved is to provide a kind of UO2-W ceramic metal ball preparation method, the method prepares UO2-W ceramic metal ball and ceramic metal W-UO2Pellet and UO2-W pellet preparation technology has a great difference, and how preparation technology difficulty (is such as prepared complete indehiscent ball, tungsten how can be allowed to be evenly distributed on UO greatly2In crystal boundary), the ceramic metal level UO prepared2-W bulb diameter is 0.05 ~ 3mm, and tungsten is evenly distributed on UO2Crystal boundary, this ceramic metal level UO2-W ball will not ftracture, and pyroconductivity is high.
This invention address that the problems referred to above be the technical scheme is that
A kind of ceramic metal level UO2The preparation method of-W ball, it specifically comprises the following steps that
The preparation of step 1 tungstenic colloidal sol: at 5 DEG C, it is 0.10��0.156 according to ammonium metatungstate/U mass ratio, carbamide/U mol ratio is that 1:4 ratio is by ammonium metatungstate, scarce uranyl nitrate solution and carbamide mixing, stir, then according to HTMA(hexamethylenamine) ratio that mol ratio is 1:4 of/U, solid HTMA(hexamethylenamine it is slowly added to when being stirred continuously), it is evenly stirred until tungstenic sol solutions transparent.
Step 2 disperses gelling: by tungstenic sol solutions by pressure venting, obtains colloidal sol and drips. Colloidal sol drips through carrier band stream carrier band, instills isooctanol equipped with heating (or paraffin oil, carbon tetrachloride CCl4) the interior balling-up under surface tension effects of dispersion column, and gelling in decline process, obtain tungstenic gel ball. For ensureing enough gelling times, dispersion column length is not less than 2m, disperse medium and isooctanol (or paraffin oil, CCl4) 65 ~ 80 DEG C should be maintained.
Step 3 is washed: being washed by tungstenic gel ball ethanol water, ethanol washing liquid concentration is 40% ~ 60%(volume ratio), scavenging period is 0.5 ~ 1h, washs three times.
Step 4 drying and calcining: tungstenic gel ball being put into follow procedure in high temperature oven and heats up, be dried calcining, gel ball completes dehydration and Organic substance skeleton subtractive process, and is converted into UO3-WO3Ball. Temperature-programmed mode is room temperature to 80 DEG C 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 is 120min ~ 150min.
Step 5 reduction sintering: by WO3-UO3Ball sinters 40-60min, WO through reduction at atmosphere of hydrogen 1300��1400 DEG C in sintering furnace3-UO3Ball is reduced into ceramic metal level W-UO2Ball. It practice, sintering time in 40-60min all can, 60min is best.
Step 6 is annealed: by ceramic metal level W-UO2Ball is CO in sintering furnace220-30min, ceramic metal level W-UO at atmosphere (1550��1600) DEG C2The tungsten of ball is by CO2Gas oxygen chemical conversion WO3, and the entrance ceramic grade UO that liquefies2Intergranular (WO3Fusing point is 1470 DEG C), obtain UO2-WO3Ball.
Step 7 is reduced: by the UO of the post liquefaction that step 6 prepares2-WO3Ball through reduction sintering 100-120min, obtains tungsten and is evenly distributed on pottery UO at sintering furnace atmosphere of hydrogen 1500��1600 DEG C2The ceramic metal level UO of crystal boundary2-W ball.
The key point of the present invention is in that how tungsten is dispersed in UO2In, the present invention is by strictly controlling the technique in preparation process, for instance sintering temperature not can exceed that 1400 DEG C, and sintering time not can exceed that 60min, the switching etc. of gas with various atmosphere in preparation process, it is possible to ensure that tungsten can be dispersed at UO2In, prepare the UO got simultaneously2-W ceramic metal ball will not be excessively fine and close because sintering, it is ensured that UO2-W ceramic metal ball will not ftracture.
To sum up, the invention has the beneficial effects as follows:
The present invention is obtained tungsten be evenly distributed on pottery UO by the preparation of tungstenic colloidal sol, dispersion gelling, washing, drying and calcining, reduction sintering, annealing, reduction2The ceramic metal level UO of crystal boundary2-W ball, the ceramic metal level UO that this method prepares2Tungsten in-W ball is evenly distributed at pottery UO2Crystal boundary, the cermet material prepared than powder method has better heat conductivity.
Accompanying drawing explanation
Fig. 1 is that W is evenly distributed on UO2Metallograph between crystal.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is done detailed description further, but embodiments of the present invention are not limited to this.
Embodiment 1:
A kind of ceramic metal level UO2The preparation method of-W ball, specifically includes following steps:
The preparation of step 1 tungstenic colloidal sol: at 5 DEG C, in 20ml acid deficient uranyl nitrate solution ([U]=500g/L), add 35.3g carbamide and 1.0g ammonium metatungstate, it is completely dissolved by stirring to solid, then HTMA(hexamethylenamine it is slowly added when being stirred continuously) 82.3g, until tungstenic sol solutions is transparent.
Step 2 disperses gelling: by tungstenic sol solutions with 0.07��0.1Mpa pressure venting, colloidal sol is by the orifice plate dispersion that diameter is 0.2mm, 0.3mm, and orifice plate vibrates and obtains colloidal sol and drip. Colloidal sol flows through dispersion orifice plate passage should be maintained at less than 5 DEG C. Colloidal sol drips through carrier band stream carrier band, instills in the isooctanol dispersion column equipped with heating or paraffin oil dispersion column, and colloidal sol drops in balling-up under surface tension effects gelling in decline process, obtains tungstenic gel ball. For ensureing enough gelling times, dispersion column length is not less than 2m, disperse medium and isooctanol (or paraffin oil) should maintain 70 ~ 80 DEG C.
Step 3 is washed: being washed by tungstenic gel ball ethanol water, ethanol washing liquid concentration is 40% ~ 60%(volume ratio), scavenging period is 0.5 ~ 1h, washs three times.
Step 4 drying and calcining: put into by tungstenic gel ball and be dried calcining in high temperature oven, gel ball completes dehydration and Organic substance skeleton subtractive process, and is converted into UO3-WO3Ball. Temperature-programmed mode is room temperature to 80 DEG C 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 is 120min ~ 150min.
Step 5 reduction sintering: by WO3-UO3Ball sinters 40-60min, WO through reduction at atmosphere of hydrogen 1300��1400 DEG C in sintering furnace3-UO3Ball is reduced into ceramic metal level W-UO2Ball.
Step 6 is annealed: by ceramic metal level W-UO2Ball is CO in sintering furnace220-30min, ceramic metal level W-UO at atmosphere (1550��1600) DEG C2The tungsten of ball is by CO2Gas oxygen chemical conversion WO3, and the entrance ceramic grade UO that liquefies2Intergranular (WO3Fusing point is 1470 DEG C), obtain UO2-WO3Ball.
Step 7 is reduced: by the UO of the post liquefaction that step 6 prepares2-WO3Ball through reduction sintering 100-120min, obtains the tungsten that diameter is 0.05��0.5mm and is evenly distributed on pottery UO at sintering furnace atmosphere of hydrogen 1500��1600 DEG C2The ceramic metal level UO of crystal boundary2-6.1m%W ball, wherein W accounts for ceramic metal ball mass fraction is 6.1%.
Embodiment 2
It is 1.56g that step 1 adds ammonium metatungstate, and all the other are with implementing 1;
Step 2 disperses gelling: tungstenic sol solutions adopts the colloidal sol that peristaltic pump obtains certain size through the dispersing head that dispersion aperture is 2mm, 4mm, 6mm drip. Colloidal sol flows through dispersion orifice plate passage should be maintained at less than 5 DEG C. Colloidal sol drips through carrier band stream carrier band, instills the CCl equipped with heating4Balling-up under surface tension effects in dispersion column, and gelling in decline process, obtain tungstenic gel ball. For ensureing enough gelling times, dispersion column length is not less than 2m, disperse medium and CCl4, 65 ~ 75 DEG C should be maintained;
Step 3 is with implementing 1;
Step 4 is with implementing 1;
Step 5 is with implementing 1;
Step 6 is with implementing 1;
Step 7 obtains, with enforcement 1, the tungsten that diameter is 0.6��3mm and is evenly distributed on pottery UO2The ceramic metal level UO of crystal boundary2-9.4m%W ball such as Fig. 1, wherein W accounts for ceramic metal ball mass fraction is 9.4%.
The ceramic metal level UO that the present invention prepares2The pyroconductivity of-W ball and other balls is more as shown in table 1:
As can be seen from the above table, the ceramic metal level UO prepared through the present invention2The pyroconductivity of-W ball prepares ceramic metal W-UO apparently higher than powder method2Fuel.
As it has been described above, the present invention can be realized preferably.
Claims (7)
1. a UO2-W ceramic metal ball preparation method, it is characterised in that specifically comprise the following steps that
A, tungstenic colloidal sol preparation: at 5 DEG C, it is 0.10��0.156 according to ammonium metatungstate/U mass ratio, carbamide/U mol ratio is that the ratio of 1:4 is by ammonium metatungstate, scarce uranyl nitrate solution and carbamide mixing, stir, then according to the mol ratio of hexamethylenamine/U is the ratio of 1:4, it is slowly added to solid hexamethylenamine when being stirred continuously, is evenly stirred until tungstenic sol solutions transparent;
B, dispersion gelling: the tungstenic sol solutions described in step a is passed through pressure venting, obtain colloidal sol to drip, colloidal sol drips through carrier band stream carrier band, instill in any one dispersion column equipped with the isooctanol of heating, paraffin oil or carbon tetrachloride, colloidal sol is made to drop in balling-up under surface tension effects, and gelling in decline process, obtain tungstenic gel ball;
C, washing: tungstenic gel ball ethanol water is washed;
D, drying and calcining: tungstenic gel ball is put into be dried in high temperature oven calcining with dehydration and elimination Organic substance skeleton take off, be finally translated into UO3-WO3Ball;
E, first time reduce sintering: by WO3-UO3Reduction sintering obtains ceramic metal level W-UO2Ball;
F, annealing: ceramic metal level W-UO2The tungsten of ball is by CO2Gas oxygen chemical conversion WO3, and the entrance ceramic grade UO that liquefies2Intergranular, obtains UO2-WO3Ball;
G, second time reduce sintering: by the UO of post liquefaction prepared for step f2-WO3Ball reduction sintering obtains ceramic metal level UO2-W ball.
2. method according to claim 1, it is characterised in that the dispersion column length in step b is not less than 2m, disperse medium and isooctanol, paraffin oil or CCl4Temperature at 65 ~ 80 DEG C.
3. method according to claim 1, it is characterised in that the ethanol washing liquid concentration volume ratio of step c washing is 40% ~ 60%, and scavenging period is 0.5 ~ 1h, washs three times.
4. method according to claim 1, it is characterized in that, the drying and calcining process of step d is: room temperature to 80 DEG C 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 is 120min ~ 150min.
5. the method according to any one of claim 1-4, it is characterised in that the condition of the reduction sintering of step e is particularly as follows: reduce at atmosphere of hydrogen 1300��1400 DEG C and sinter 40-60min.
6. method according to claim 5, it is characterised in that step f is at CO2Under atmosphere, by ceramic metal level W-UO2Ball puts in sintering furnace, sinters 20-30min at 1550��1600 DEG C.
7. method according to claim 6, it is characterised in that the condition of the reduction sintering of step g is particularly as follows: sinter 100-120min through reduction at atmosphere of hydrogen 1500��1600 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107256726A (en) * | 2017-07-03 | 2017-10-17 | 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3429699A (en) * | 1967-07-24 | 1969-02-25 | Atomic Energy Commission | High loaded uo2-columbium cermets |
| US3759787A (en) * | 1960-09-30 | 1973-09-18 | Nasa | Nuclear fuel elements |
| 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 |
| CN1062126A (en) * | 1990-11-30 | 1992-06-24 | 清华大学 | Use nuclear fuel micro ball prepared by full gelatinizing method |
| CN100999408A (en) * | 2006-12-15 | 2007-07-18 | 清华大学 | Method of preparing UO2 ceramic fuel microsphere |
| CN101172660A (en) * | 2007-10-12 | 2008-05-07 | 清华大学 | Method for producing high temperature reactor fuel element UO* 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 |
-
2016
- 2016-01-29 CN CN201610062445.1A patent/CN105642907B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| GB1165866A (en) * | 1967-07-24 | 1969-10-01 | Atomic Energy Commission | 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 |
| CN1062126A (en) * | 1990-11-30 | 1992-06-24 | 清华大学 | Use nuclear fuel micro ball prepared by full gelatinizing method |
| CN100999408A (en) * | 2006-12-15 | 2007-07-18 | 清华大学 | Method of preparing UO2 ceramic fuel microsphere |
| CN101172660A (en) * | 2007-10-12 | 2008-05-07 | 清华大学 | Method for producing high temperature reactor fuel element UO* 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 |
Non-Patent Citations (2)
| Title |
|---|
| GERDES, R. J.等: "Refractory Oxide-Metal Composites: Scanning Electron Microscopy and X-Ray Diffraction of Uranium Dioxide-Tungsten", 《SCIENCE》 * |
| 徐志昌: "陶瓷核燃料UO2微球的制造", 《94"全国结构陶瓷、功能陶瓷、金属/陶瓷封接学术会议论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107256726A (en) * | 2017-07-03 | 2017-10-17 | 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 |
| 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 |
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