CN102240812B - Preparation method for uranium molybdenum alloy powder - Google Patents
Preparation method for uranium molybdenum alloy powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910001182 Mo alloy Inorganic materials 0.000 title abstract description 10
- KTEXACXVPZFITO-UHFFFAOYSA-N molybdenum uranium Chemical compound [Mo].[U] KTEXACXVPZFITO-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 229910008894 U—Mo Inorganic materials 0.000 claims description 94
- 230000004913 activation Effects 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 63
- 230000008569 process Effects 0.000 abstract description 26
- 239000002245 particle Substances 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract description 8
- 239000003758 nuclear fuel Substances 0.000 abstract description 5
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 25
- 238000005984 hydrogenation reaction Methods 0.000 description 20
- 238000001994 activation Methods 0.000 description 19
- 229910052770 Uranium Inorganic materials 0.000 description 13
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 13
- 238000006356 dehydrogenation reaction Methods 0.000 description 12
- 239000000956 alloy Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- AILDTIZEPVHXBF-UHFFFAOYSA-N Argentine Natural products C1C(C2)C3=CC=CC(=O)N3CC1CN2C(=O)N1CC(C=2N(C(=O)C=CC=2)C2)CC2C1 AILDTIZEPVHXBF-UHFFFAOYSA-N 0.000 description 3
- 244000308495 Potentilla anserina Species 0.000 description 3
- 235000016594 Potentilla anserina Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000711 U alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003471 anti-radiation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000006101 laboratory sample Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003434 inspiratory effect Effects 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a preparation method for uranium molybdenum alloy powder, and the method is used for preparing the uranium molybdenum alloy powder meeting the demand on a certain particle size and belongs to the field of nuclear technique application. The preparation method provided by the invention mainly comprises the following steps of: cleaning and activating before activating the uranium molybdenum alloy. By cleaning the uranium molybdenum alloy with aqua regia, distilled water, absolute ether, absolute ethyl alcohol, and the like, an oxide layer on the surface of the uranium molybdenum alloy can be efficiently removed, thereby achieving the clean surface of the uranium molybdenum alloy before absorbing hydrogen. Parameters of an activating process are efficiently controlled, thereby accurately controlling the particle size of the uranium molybdenum alloy powder. The preparation method for the uranium molybdenum alloy powder provided by the invention has the characteristics of less working procedures, simple process, small investment, and the like, and is suitable for being applied to the field of nuclear fuel cycle.
Description
Technical field
The invention belongs to the nuclear material preparing technical field, be specifically related to a kind of preparation method of U-Mo Alloy powder, the present invention prepares required for the preparation of hybrid reactor porous U-Mo Alloy fuel element and satisfies the U-Mo Alloy powder that certain particle diameter requires.
Background technology
In the natural calculus-dissolving energy day by day exhausted today, nuclear energy has occupied more and more consequence.The operation technique of fission nuclear fuel is quite ripe at present, and this wherein is most widely used based on the nuclear fuel of uranium element.Yet common metallic uranium is being the α phase below 668 ℃, and corrosion resistance and anti-radiation performance are all very poor.In order to improve the irradiation stability of fuel, usually adopt in metallic uranium, to add a small amount of alloying element, form the uranium alloy material that acts as a fuel.
Be that γ solid solution occupies very wide temperature range and concentration range in the alloy at the uranium molybdenum.Add a certain amount of molybdenum and help that the low temperature direction is stable in opposite directions with the γ of cubic structure, obtain each to same lattice structure, thereby strengthen the anti-radiation performance of uranium.In addition, the U-Mo Alloy of certain ingredients can form multiple metastable phase under the specific heat treatment process conditions.In changing U-Mo Alloy, when the content of molybdenum and Technology for Heating Processing, might in very wide scope, change composition, the tissue of phase, and then physical property and the mechanical property of change alloy, this has important practical significance.
At RERTR plan (Reduced Enrichment for Research and Test Reactors, the planning of experiments of reduction research and test reactor fuel enrichment) under the support, U.S.'s fuel U-Mo Alloy that began one's study from 1996, leading is Argonne National Laboratory, and Idaho National Laboratory, Oak Ridge National Laboratory, Y-12 factory also have some Fuel Tech. Inc. that participation is arranged.Early stage research starts from design and the checking of alloying component.Analysis through irradiation examination and other means was locked as U-7Mo and U-10Mo gradually to the goal in research of dispersion fuel afterwards.Russia, France, Argentina, Korea S etc. have also all carried out the research of U-Mo Alloy as reactor fuel subsequently.
The preparation of dispersion fuel with uranium fuel material powder as the basis.The efflorescence technique of the uranium dioxide of using in the tradition nuclear power industry and the inter-metallic compound material of uranium is comparatively ripe.Their mechanical milling methods that adopt because they are generally more crisp, get up to have no difficulty so grind more.But this technique is difficult to be applied directly in the powder preparation of U-Mo Alloy fuel material, and a most important reason is exactly, and U-Mo Alloy shows very strong metalline, and its plasticity is more much better than the inter-metallic compound material of uranium dioxide and uranium.Proposed gradually again afterwards hydrogenation and dehydrogenization method and atomization, rear two kinds of methods are owing to introducing the less advantage that has more of impurity.
Atomization comprises the jet atomization method, the centrifugal atomizing method, and rotation electrode atomization etc., its principle is by mechanical means molten alloy to be separated cooling to form spherical powder.In the atomization method of having studied, the most successful with the centrifugal atomizing technique of Korea S's exploitation
[1]The concrete grammar of this technique is as follows: metal uranium button and the molybdenum piece (U-2Mo and U-10Mo have been used in initial research) that will design proportioning place the graphite crucible that has applied refractory ceramics, use induction melting.The molten metal of melting is poured on the graphite disk of a lower rapidly rotation of argon atmospher protection by an aperture.Drop is subjected to centrifugal action to disperse to fly out curing, falls subsequently in the funnel-form collecting tank of container bottom.In the experimentation, the rotary speed of rate of feeding and disk is most important for the control of finished product powder size and dimension, need to be adjusted to suitable parameter to optimize powder morphology.The outstanding advantages of this method is that the gained powder is approximately sphere, smooth surface, but the method initial investment is huge.
As far back as the fifties in last century, the hydrogenation and dehydrogenization method just is employed the production with the metallic uranium powder, and the method is considered to the method for a kind of extraordinary preparation ultra-fine (generally below 38 μ m) powder.Its technological process is as follows: the U-Mo Alloy block is heated (generally be lower than 300 ℃) under suitable temperature uranium meeting and hydrogen reaction, the hydride density (10.9g/cm of uranium under nitrogen atmosphere
3) than metallic uranium density (about 19g/cm
3) much lower, meeting progressively splits away off from block with the form of hydride powder under effect of stress.After hydrogenation is finished, the hydride powder is heated under vacuum, hydrogen can dissociate gradually and emit, and stays at last the powder of uranium alloy.
Under 250 ℃ hydrogenation temperature,
The hydrogen-absorption speed ratio of phase U-Mo Alloy
Mutually much lower.Hydrogenation kinetics curve by different phase structure U-Mo Alloys can be found out, contains
More U-Mo Alloy hydrogenation is faster mutually.Therefore, wish obtains by hydrogenization method
Phase U-Mo Alloy powder need be taked usually such as step: at first alloy is obtained suitable phase structure by heat treatment; Secondly by the efflorescence of hydrogenation dehydrogenation technique; Allow the powder answer be by suitable heat treatment measure at last
Phase.
The people such as Argentine Balart described the hydrogenation dehydrogenation technique that they use in detail in one piece of report in 2000.Here they have utilized U-Mo Alloy
The easier characteristic that is hydrogenated mutually, at first with certain heat treatment make U-Mo Alloy (
Phase) grain boundaries is separated out
Phase is by right
The hydrogenation of phase makes U-Mo Alloy separately efflorescence between crystal boundary.Behind dehydrogenation, by heat treatment the U-Mo Alloy powder is replied again
Phase.The U-Mo Alloy composition that uses in the experiment is U-7Mo and U-8Mo, and the author thinks that containing the U-Mo Alloy of molybdenum between 5 ~ 8% is more suitable in this technique because they with heat treatment occur to
The phase transformation of phase is relatively easy.Can infer a crystal grain of block materials before each particle is equivalent in the powder that obtains by this method.So be easy to expect, can control by controlling raw-material grain size the size distribution of powder.The people such as Argentine Balart in 2002 obtain the U-Mo Alloy of different grain sizes by heat treatment, and then the hydrogenation dehydrogenation obtains powder as stated above, has realized the rough control that powder size is distributed.
The people such as Argentine Pasqualini had also developed another kind of hydrogenation dehydrogenation method in 2002
[7]The places different from top method are that the method does not have before
Heat of transformation processing procedure directly allows metastable state
The alloy hydride of phase.This hydride particle is larger, thus also need a process of lapping to make it fragmentation, dehydrogenation then.This technique is known as HMD(Hydriding-milling-dehydriding) technique, i.e. hydrogenation-grinding-dehydrogenation technique.HMD technique at first needs one to inhale hydrogen activation process.At first the U-7Mo alloy is heated to 700 ℃ of insulations about 1 hour under 1bar hydrogen pressure.This process has guaranteed that alloy cube matherial can be by uniform hydrogenation, but its mechanism it be unclear that.The residual stress that comes from casting technique is very large to this process influence, is in the situation of compression on the surface especially, and suction hydrogen effect is bad.After this be only formal hydrogenation process, hydrogenation temperature can be between 50 ℃～190 ℃, but the fastest hydrogen-absorption speed occurs in 120 ℃.Hydrogen pressure remains on below the 2atm, and along with the rising of hydrogen pressure, hydrogen-absorption speed also can increase.Under suitable condition, the fastest hydrogen-absorption speed can reach 1lt/min.kg.The product of this moment is generally the particle about 5mm, and chemical formula can be used MH
3-xExpression, wherein M represents the U-7Mo alloy, x is generally less than 0.5.Because such particle is the hydrogenation phase of fragility, therefore can pass through the further fragmentation of process of lapping.The size distribution of powder can be similar to by processing parameter and control.For avoiding the spontaneous combustion of hydride, whole technique is carried out (oxygen content is lower than 5%) in the hypoxemia glove box.The dehydrogenation process is carried out under 700 ℃ vacuum atmosphere.It should be noted that before being exposed to powder in the air, carry out first a step pre-oxidation passivating process (expose a hour in 25% air, 75% argon gas, 50% air, 50% argon gas exposes a hour again), in order to avoid unexpected a large amount of oxidations cause spontaneous combustion.
Contemporaneity, Russia also is studied hydrogenation dehydrogenation technique, and what they used is to contain the molybdenum amount at a series of U-Mo Alloys of 1.9 wt.%～9.5wt.%.Different from Argentine technique, they at first will
The U-Mo Alloy of phase is converted into fully by heat treatment
Mutually and
' phase (U
2Mo) then duplex structure carries out the hydrogenation dehydrogenation, by a quenching process powder is replied at last to be
Phase.Result of study shows that the size distribution of U-Mo Alloy powder is relevant with molybdenum content, and along with the rising of molybdenum content, coarse grained share also can increase in the U-Mo Alloy powder.If powder particle is too thick, also can do again the several times circulation of hydrogenation dehydrogenation, particle size can further reduce.Interpolation aluminium and tin will make powder fining more easy in U-Mo Alloy.
By top analysis, we can find out adopt the standby metallic uranium powder technical maturity of hydrogenation and dehydrogenization legal system, equipment investment is few and the powder that makes in to introduce impurity less; Foreign study person's work shows can adopt the method to prepare the U-Mo Alloy powder, and can obtain by the cycle-index of controlling raw-material grain size or hydrogenation dehydrogenation the powder body material of varying particle size.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of U-Mo Alloy powder.
The preparation method of U-Mo Alloy powder of the present invention in turn includes the following steps:
1), the cleaning before the activation
Nitric acid and hydrochloric acid are mixed with wang aqueous solution according to the ratio of 1:3, U-Mo Alloy are placed wang aqueous solution, until U-Mo Alloy becomes silvery white by original grey black; The U-Mo Alloy taking-up is cleaned with distilled water, absolute ethyl alcohol, absolute ether successively; Under argon shield atmosphere, cleaned U-Mo Alloy is transferred in the reactor;
2), the preliminary treatment before the U-Mo Alloy activation
Reactor is evacuated to 50Pa, then is heated to 250 ℃, is evacuated to 4Pa again and keeps 30min; U-Mo Alloy after the heating is continued to be heated to 650 ℃, continue to be evacuated to 4Pa and keep 1h, be cooled to room temperature;
3), U-Mo Alloy powder preparation
The high-purity hydrogen of 0.2MPa～1.0MPa pressure passed into step 2 is housed) in the reactor of the U-Mo Alloy that preliminary treatment is good; Obtain the hydrogen－sucking amount of U-Mo Alloy according to the numerical value change of the pressure sensor of reactor setting, according to required U-Mo Alloy granularity requirements, determine that U-Mo Alloy inhales the cycle-index of putting hydrogen.
Cleaning before the activation of U-Mo Alloy among the preparation method of the present invention can be removed the impurity on surface effectively, guarantees the surface that has relative cleaning before the U-Mo Alloy activation, simultaneously, can reduce bibliographical information about carrying out before the U-Mo Alloy activation
In opposite directions
The converting process of phase has reduced the manufacturing cycle of U-Mo Alloy powder widely, has simplified activating process, has reduced the cost of preparation U-Mo Alloy powder;
Pretreating process before the U-Mo Alloy activation comprises cold degasification, the hot degasification before the activation.By to laboratory sample cold/hot degassing processing, can remove the oxide impurity of U-Mo Alloy adsorption, avoid in heating process, forming oxide, reduce the hydrogen-absorption speed of sample.By the hot degassing processing to laboratory sample, can effectively remove micro-moisture is inhaled the hydrogen process on U-Mo Alloy impact.
U-Mo Alloy must keep 30min to hydrogen and the constant temperature that is filled with certain pressure in the reactor that fills U-Mo Alloy in advance before inhaling the hydrogen activation and through after the preliminary treatment, can further eliminate the U-Mo Alloy surface impurity to the impact of U-Mo Alloy powder preparation.
The invention has the beneficial effects as follows the production cycle that has shortened the preparation of U-Mo Alloy powder, simplified activating process, reduce the preparation cost of U-Mo Alloy powder, can effectively control the granularity of U-Mo Alloy powder.
The specific embodiment
The preparation method of U-Mo Alloy powder of the present invention, its cleaning process is mainly carried out successively by following four steps: 1) the U-Mo Alloy sample is placed red fuming nitric acid (RFNA) and concentrated hydrochloric acid (volume ratio 1:3) mixed solution, its objective is the oxide layer of removing the surface, this step is relatively more crucial, directly affect the cleaning quality of U-Mo Alloy sample, also affect in the subsequent technique U-Mo Alloy and whether can inhale the hydrogen activation; 2) the U-Mo Alloy sample after the pickling is placed distilled water, its objective is and remove the residual acid solution of U-Mo Alloy sample surfaces; 3) the U-Mo Alloy sample after the depickling is placed absolute ether, its purpose is removed the moisture on surface; 4) the U-Mo Alloy sample with depickling, dehydration places absolute ethyl alcohol, its objective is the greasy dirt of removing the surface; 5) under Ar gas protection, the U-Mo Alloy sample after depickling, dehydration, the de-oiling placed reactor and carries out sealing after the access activation system carry out subsequent treatment.
Activation system mainly is made of reactor, standard can, gas tank, pressure sensor, valve and data collecting system etc.Whole activating process system before use must be through helium mass spectrum leak detection, leak rate should less than
The main splendid attire of reactor U-Mo Alloy block to be activated; Standard can is mainly used in U-Mo Alloy and inhales the quantitatively calibrating put inspiratory capacity and discharge quantity in the hydrogen; Gas tank is mainly used in the collection of gas flow in the deflation course; Pressure sensor is mainly used in the pressure that U-Mo Alloy puts in the hydrogen process in suction and shows and control; Valve is mainly controlled process system; Data collecting system is mainly used in the Real-time Collection of data in the U-Mo Alloy powder preparation process and the activating process parameter of U-Mo Alloy arranges.
The concrete preparation process of U-Mo Alloy powder of the present invention is as follows:
Cleaning before the U-Mo Alloy activation provided by the present invention.Its cleaning process is mainly carried out successively by following four steps: 1) the U-Mo Alloy sample is placed red fuming nitric acid (RFNA) and concentrated hydrochloric acid (volume ratio 1:3) mixed solution, its objective is the oxide layer of removing the surface, this step is relatively more crucial, directly affect the cleaning quality of U-Mo Alloy sample, also affect in the subsequent technique U-Mo Alloy and whether can inhale the hydrogen activation; 2) the U-Mo Alloy sample after the pickling is placed distilled water, its objective is and remove the residual acid solution of U-Mo Alloy sample surfaces; 3) the U-Mo Alloy sample after the depickling is placed absolute ether, its purpose is removed the moisture on surface; 4) the U-Mo Alloy sample with depickling, dehydration places absolute ethyl alcohol, its objective is the greasy dirt of removing the surface; 5) under Ar gas protection, the U-Mo Alloy sample after depickling, dehydration, the de-oiling placed reactor and carries out sealing after the access activation system carry out subsequent treatment.
Pretreating process before the sample activation directly affects the hydrogen-absorption speed of sample, by experiment, has determined following pretreating process: 1) at room temperature with pump reactor is evacuated to below the 50Pa, its objective is the adsorption material of removing sample; 2) reactor is heated to 250 ℃ and with pump depletion to the 4Pa and keep 30min, its objective is the removal of carrying out moisture content; 3) sample is continued to be heated to 650 ℃ and be evacuated to below the 4Pa and keep 1h, its purpose mainly is the cubical expansion explosion by sample, removes the oxide of surface trace and exposes unsalted surface, guarantees the quick suction hydrogen of next step sample.
Be provided with four kinds of activating process parameters (seeing Table 1) in the experiment.From hydrogen-absorption speed, under the A condition, U-Mo Alloy sample hydrogen-absorption speed is quite slow, and after the activation, the size distribution of sample is with greater than 150
Granule number in the majority, under the condition D, the hydrogen-absorption speed of U-Mo Alloy sample is very fast, and the activation after, the size distribution of sample is 100
With 150
Granule number in the majority.
Table 1 cleaning and activation parameter
| Condition | Cleaning | Charge/g | Hydrogen uptake condition | Cycle-index |
| A | Rare nitric acid+water+ether+ethanol | 43 | 0.4MPa; Room temperature | 5 |
| B | Chloroazotic acid+water+ether+ethanol | 100 | 0.5MPa；80℃ | 10 |
| C | Chloroazotic acid+water+ether+ethanol | 120 | 1.0MPa；80℃ | 15 |
| D | Chloroazotic acid+water+ether+ethanol | 150 | 1.0MPa；80℃ | 20 |
Technical process major technique condition
Nitric acid and hydrochloric acid mixed solution: volume ratio: 1:3, temperature: 35 ℃～40 ℃;
Absolute ether: analyze pure, normal temperature;
Absolute ether: analyze pure, normal temperature;
Cold degassing processing: normal temperature, be evacuated to 2～4Pa and keep 30min;
Hot degassing processing: 250 ℃, be evacuated to 2～4Pa and keep 30min;
Pressurize is processed under the hydrogen atmosphere: 650 ℃, be evacuated to 2～4Pa and keep 60min after filling hydrogen 1atm;
The hydrogen circular treatment is put in suction: inhale the hydrogen temperature: normal temperature～80 ℃; Inhale hydrogen pressure: 5atm～10atm; Hydrogen discharging temperature: 500 ℃～600 ℃;
The hydrogen cycle-index is put in suction: can carry out concrete setting by U-Mo Alloy powder granularity according to actual needs.
Claims (1)
1. the preparation method of a U-Mo Alloy powder is characterized in that, described preparation method in turn includes the following steps:
1), the cleaning before the activation
Nitric acid and hydrochloric acid are mixed with wang aqueous solution according to the ratio of 1:3, U-Mo Alloy are placed wang aqueous solution, until U-Mo Alloy becomes silvery white by original grey black; The U-Mo Alloy taking-up is cleaned with distilled water, absolute ethyl alcohol, absolute ether successively; Under argon shield atmosphere, cleaned U-Mo Alloy is transferred in the reactor;
2), the preliminary treatment before the U-Mo Alloy activation
Reactor is evacuated to 50Pa, then is heated to 250 ℃, is evacuated to 4Pa again and keeps 30min; Continue to be heated to 650 ℃, continue to be evacuated to 2 ~ 4Pa and fill under the hydrogen 1atm keep 60min after, be cooled to room temperature;
3), U-Mo Alloy powder preparation
The high-purity hydrogen of 0.2MPa～1.0MPa pressure passed into step 2 is housed) in the reactor of the U-Mo Alloy that preliminary treatment is good; Obtain the hydrogen－sucking amount of U-Mo Alloy according to the numerical value change of the pressure sensor of reactor setting, according to required U-Mo Alloy granularity requirements, determine that U-Mo Alloy inhales the cycle-index of putting hydrogen.
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| CN102764894B (en) * | 2012-07-30 | 2014-10-29 | 四川材料与工艺研究所 | Method for preparing high-purity vanadium powder |
| CN103706801B (en) * | 2013-12-26 | 2016-05-25 | 四川材料与工艺研究所 | The preparation method of uranium zircaloy powder |
| CN105328196B (en) * | 2015-11-02 | 2017-03-22 | 中国核动力研究设计院 | U-Mo alloy powder manufacturing process for controlling nitrogen content |
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