CN106219609B - Liquid crystal irradiation prepares hollow UO2The method of nanosphere - Google Patents
Liquid crystal irradiation prepares hollow UO2The method of nanosphere Download PDFInfo
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- C01G43/00—Compounds of uranium
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- C01P2004/30—Particle morphology extending in three dimensions
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Abstract
Hollow UO is prepared the invention discloses a kind of irradiation of liquid crystal2The method of nanosphere, has been prepared by 1~10nm of particle diameter UO by the γ hexagonal phase liquid crystal systems for irradiating Triton X 100/AUC solution composition2Molecular 10~the 100nm of diameter of nanoparticle, 5~45nm of wall thickness hollow UO2Nanosphere.And find that the product can be stabilized at 300 DEG C.Can be with the hollow UO of Effective Regulation by regulating and controlling close rate and the concentration of Triton X 1002The cavity size and wall thickness of nanosphere.
Description
Technical field
The present invention relates to the preparation of uranium oxide nano material, and in particular to hollow UO2The preparation method of nanosphere.
Background technology
Uranium oxide, such as UO2、U3O8、UO3, it is important nuclear fuel, while the still effective catalyst of a class.For example
U3O8Can be for chloride organic micromolecule compound of degrading[1]；UO2Can be with catalytic oxidation of alcohol[2]；UO3Acetaldehyde system can be catalyzed
Standby furans[3].In closely about ten years, there are some researches show nano-scale uranium oxide has very low sintering temperature[4]With efficiently urge
Change activity[5 , 6].Therefore, uranium oxide nano material of the synthesis with specific dimensions pattern causes extensive concern.At present, as quasi- ball
Shape UO2Nano particle[6-9]、U3O8Nano flower[5]、U3O8Nanometer rods[6,10], mesoporous U3O8Particle[11]、U3O8Nanotube/line[12]And
The uranium oxide micro/nano material of other labyrinths[5,10,13,14]Prepared by heat chemistry and electrochemical process.It is empty
Heart nano material is based on its controllable structurally and mechanically property, huge surface area and penetration property, in gas held, catalysis etc.
Aspect causes broad interest[15-17], and hollow Nano nuclear material is because that can accommodate the gas of nuclear fission generation and very attractive.But
It is up to the present, except the hollow UO prepared before us by solution irradiation method2Nanosphere[18]Outside, other synthesis be yet there are no empty
The report of heart uranium oxide nano material.
Lysotropic liquid crystal is typically what is be mixed to form according to a certain percentage by surfactant and water, with stratiform, six sides, is stood
The isostructural phase in side.Based on its unique internal order structure, it is widely used in drug delivery[19], material prepare[20]Deng side
Face.In terms of material preparation, by chemistry and electrochemical method, lysotropic liquid crystal, which is widely used for preparing, has ordered network and Jie
The homogeneous mesoporous material in hole[21], nano thin-film[22], nanometer rods/line[23]Deng.Zhu etc.[24]Report and prepared using layered liquid crystal
Laminar nano layer material is obtained, then hollow Nano tube material is obtained by curling.Zhang etc.[25]Then by AOT/H2O stratiform liquid
Crystalline substance is in supercritical CO2In the presence of, it is changed into spherical micelle, hollow silicon oxide nano sphere is prepared as template.Directly
It is a challenging problem to connect and prepare hollow nano-sphere using liquid crystal.
Ionising radiation (such as gamma-rays, electron beam) is widely used in nano material preparation[26].Jiang etc.[27]Report
Using γ irradiation by polyoxyethylene (10) ether, n-hexane, n-hexyl alcohol/isopropanol (2:1), the anti-hexagonal phase liquid crystal of aqueous phase formation
System prepares ZnS nano wires.The report that liquid crystal Method and ionization radiation method are combined into preparation nano material at present only has this piece.
Therefore, it is necessary to expand its application.In addition, UO can be prepared using ionizing radiation uranyl nitrate system2It is molten
Glue[28,29].But Rath etc.[28]It was found that the UO that the system is prepared2Nano-particle is oxidized easily in atmosphere.
In work before, we are obtained using gamma-ray irradiation ammonium uranyl tricarbonate (AUC) and ammonium formate mixed solution
To it is stable, can 450-600 DEG C of sintering UO2Nano-particle[30].Further by reducing the dense of ammonium uranyl tricarbonate
Degree, with generated in-situ H2Bubble is that hollow UO is made in template2Nanosphere[18].The method is simple, do not introduce impurity, but due to
The poor rigidity of bubble template, gained nanosphere it is in irregular shape, the size of its cavity also is difficult to regulate and control.Here, we utilize
The Triton X-100 liquid crystal system regulation and control that gamma-ray irradiation contains ammonium uranyl tricarbonate prepare hollow uranium oxide nanosphere.
The content of the invention
It is an object of the invention to provide one kind hollow UO is prepared based on irradiation method regulation and control2The method of nanosphere, for
The research in the field such as nuclear fuel and catalysis.
The hexagonal phase liquid crystal system that the present invention is constituted using gamma-rays or electron beam irradiation Triton X-100/AUC solution,
Obtained by regulating and controlling the conditions such as absorbed dose of radiation, close rate and Triton X-100 contents by UO2Self-assembly formation
Hollow UO with certain size and wall thickness2Nanosphere.Specifically, the technical scheme is that：
A kind of hollow UO2The preparation method of nanosphere, comprises the following steps：
1) compound concentration >=2mmolL-1UO2(CO3)3 4-Alkaline solution；
2) in UO2(CO3)3 4-Triton X-100 are added in alkaline solution to be well mixed, and form hexagonal phase liquid crystal system；
3) under an inert atmosphere, to step 2) system close rate is carried out with gamma-rays or electron beam for 40~70Gy
min-1Irradiation, obtain black precipitate, through centrifugation, washing, dry, obtain hollow UO2Nanosphere.
Above-mentioned steps 1) in, the UO2(CO3)3 4-PH >=8 of alkaline solution, wherein UO2(CO3)3 4-Concentration it is further
Preferably 2~20mmolL-1。
It is preferred that, step 1) solution be to form ammonium uranyl tricarbonate (AUC) and alkaline matter mixed preparing, for example will
AUC and Na2CO3It is configured to mixed solution.Wherein, AUC is obtained from the conversion of uranium raw material, and the uranium raw material can include lithium
Uranium UF6, uranyl nitrate UO2(NO3)2、UO2(NO3)22TBP and/or UO2F2Deng the various raw materials containing U (VI), pass through NH3And CO2
Double gas lead to method or add (NH4)2CO3And NH4HCO3Method prepares AUC.
Step 2) UO2(CO3)3 4-In Triton X-100 mixed system, Triton X-100 contents 35~
65wt%.
It is preferred that, step 2) Triton X-100 are added into UO2(CO3)3 4-After in alkaline solution, heating stirring mixing is equal
It is even, it is then centrifuged for removing bubble.
Step 3) irradiation carry out under inert atmosphere conditions, such as being passed through nitrogen, argon gas；Irradiation bomb can be electronics
Accelerator or all kinds of gamma ray projectors.Irradiation dose is preferably 4~50kGy.
In the certain preferred embodiments of the present invention, step 3) use 40~70Gymin-1Close rate irradiation 50~
1250min。
The present invention typically synthesizes hollow UO2The process of nanosphere is：Prepare and contain 2~20mmolL-1AUC, 6~
60mmol·L-1Na2CO3Solution, then add certain mass Triton X-100, by solution move into irradiation tube in, heating
To 40 DEG C, magnetic agitation is well mixed, and is then centrifuged for removing bubble；Logical N2Tube sealing after a period of time；With 40~70Gymin-1
Close rate irradiate 50~1250min (close rate is determined by ferrous sulfate dosimeter), obtain black UO2Precipitation.
The present invention has been prepared by grain by irradiating the hexagonal phase liquid crystal system that Triton X-100/AUC solution is constituted
1~10nm of footpath UO2Molecular 10~the 100nm of diameter of nanoparticle, 5~45nm of wall thickness hollow UO2Nanosphere, it is furthermore preferred that
It is by the molecular 60~80nm of diameter of particle diameter 3~5nm nanoparticles, 10~20nm of wall thickness hollow UO2Nanosphere.Present invention system
Standby hollow UO2Nanosphere can be stabilized at 300 DEG C.Can be effective by regulating and controlling close rate and Triton X-100 concentration
Regulate and control UO2Whether nanosphere is hollow-core construction and wall thickness.
The technical advantage of the present invention is mainly reflected in the hollow UO of gained2The regular shape of nanosphere, the size of its cavity and
Wall thickness can be with conveniently regulating and controlling.
Brief description of the drawings
Fig. 1, different liquid crystal systems petrographic microscope (POM) figure (× 200), wherein：(a) it is respectively 50wt% with (b)
POM figures after TritonX-100/AUC solution predoses, (c) and (d) is respectively 60wt% and 70wt%Triton X-100/
The POM figures of AUC solution systems；Radiation dose rate 40Gymin-1, accumulated dose is 12kGy.
Fig. 2, difference Triton X-100/H2The POM figures for the system that O is constituted, wherein Triton X-100 contents：(a)
40wt%, (b) 50wt%, (c) 60wt%.
Small angle X ray scattering (SAXS) data of liquid crystal system after Fig. 3, predose, wherein：(a) predose, (b) irradiation
Afterwards；Triton X-100 contents：50wt%, close rate 40Gymin-1, accumulated dose 12kGy.
The POM figures of Fig. 4,40wt%Triton X-100/AUC systems.
Fig. 5,50wt%Triton X-100/AUC liquid crystals tie up to 40Gymin-1Under the conditions of irradiation 300min obtained by produce
TEM figures (a and c), SEM figures (b) and the HRTEM figures (d) of thing, wherein the illustration of (c) figure is schemed for the SAED of the sample.
Powder X-ray RD before and after the product heat treatment that the irradiation of Fig. 6,50wt%Triton X-100/AUC liquid crystal system is obtained
Figure, wherein：(a) it is reduced directly in products therefrom, (b) 300 DEG C of air and is heat-treated 3 hours products therefroms.
Fig. 7,50wt%Triton X-100/AUC liquid crystals tie up to 40Gymin-1Under the conditions of irradiation 300min obtained by produce
The TEM figures of thing after heat treatment, illustration is schemed for the SAED of the product.
Fig. 8,50wt%Triton X-100/AUC liquid crystals tie up to the TEM of irradiation products therefrom under the conditions of Different Dose Rates
Figure, wherein：(a)200Gy·min-1,(b)100Gy·min-1,(c)70Gy·min-1,(d)12Gy·min-1；Accumulated dose
12kGy。
Fig. 9, difference Triton X-100/AUC system irradiation products TEM figures, wherein Triton X-100 contents:(a)
25wt%, (b) 45wt%, (c) 55wt%and (d) 70wt%；Close rate 70Gymin-1, accumulated dose 12kGy.
The hydrodynamic radius distribution map of Figure 10,25wt%Triton X-100/AUC systems.
Figure 11, hollow UO2The formation mechenism schematic diagram of nanosphere.
Embodiment
First, experimental method
1. experiment reagent
UO2(NO3)2·6H2O, GR, Chemapol, Prague Czechoslovakia.NH4HCO3、Na2CO3, ammonium formate
(HCOONH4) it is that analysis is pure, directly use.Experimental water is ultra-pure water.
2. the synthesis of ammonium uranyl tricarbonate
According to bibliography[31], by UO2(NO3)2·6H2Heat treatment obtains Huang in 3 hours to O under the conditions of 350 DEG C in Muffle furnace
Color orange oxide powder.Under 60 DEG C of water-baths, by a certain amount of saturation NH4HCO3Solution is slowly dropped to containing UO3Round-bottomed flask
In, stirring is until yellow solid all dissolves, and suction filtration, moves into cooling and standings in beaker by filtrate and crystallize while hot.Collected by suction is brilliant
Body, and use 3wt%NH4HCO3Washing, vacuum drying obtains uranium carbonate acid amides (AUC).Elementary analysis result shows that products therefrom is
(NH4)4[UO2(CO3)3](Mr=522.21).Elementary analysis result (%)：C 6.90, H 3.09, N 10.73；Theoretical value
(%)：C 6.87, H 3.09, N10.70.
3.UO2The preparation of nano particle
Prepare and contain 5mmolL-1AUC、15mmol·L-1Na2CO3Solution.By above-mentioned solution and certain mass
TritonX-100 immigrations irradiation tube (In 15mm), 40 DEG C are heated to, magnetic agitation is well mixed, are then centrifuged for removing bubble.
Logical N2After 20min, tube sealing.Sample is placed in cobalt source (3 × 104Ci in) position of given dose rate irradiated (close rate by
Ferrous sulfate dosimeter is determined), obtain black precipitate.Other samples are synthesized by changing Triton X-100 concentration, close rate
Product.
4. Characterization of The Products
Liquid crystal after predose and irradiation is tied up to its POM image is surveyed on Leica DMLP petrographic microscopes, and 18
DEG C with AntonPar SAXSess small-angle scatterings instrument (SAXS) characterize.25wt%Triton X-100 and AUC system 25 DEG C with
Malvern Nano ZS90 dynamic light scatterings, 90 ° of angle of scattering, 4mW He-Ne lasing light emitters, in 10000rmp centrifugations before measurement
30min.Black precipitate is fully washed, centrifuged by the sample with ethanol dissolving after irradiation, centrifugation with water, and room temperature in vacuo is dry
To solid powder.Clean sample dispersion will be centrifuged in ethanol, drop in and be coated with the copper mesh of carbon film, spontaneously dry at room temperature
Electron microscopic sample is made, is scanned with the Tecnai G2T20 types transmission electron microscopes (TEM) and Nova Nano SEM430 of FEI Co. of the U.S.
Electronic Speculum (SEM) observes its pattern, and operating voltage is respectively 200 and 15kV.SEAD (SAED) is surveyed with TEM instrument.Particle
Size tries to achieve average value by counting 100 particles.
Product vacuum heat treatment experiment is carried out in 1200 DEG C of open-type vacuum/air electric tube furnaces, and heating mode is journey
Sequence heats up.Powder x-ray diffraction (XRD) is characterized by Rigaku Dmax-2000 diffractometers and (uses CuKαTarget, λ=
0.15418nm)。
2nd, experimental result and discussion
1. the sign of liquid crystal phase
Beyer have studied Triton X-100/D using two-dimentional nuclear-magnetism means2O binary systems with temperature phasor[32]。18
At DEG C, when Triton X-100 contents are 40-60wt%, the system is hexagonal phase structure；Triton X-100 contents exist
During 70wt%, temperature can form layered liquid crystal less than 8 DEG C.
The system that pure water is mixed with 50wt%Triton X-100 is replaced using AUC solution, passes through polarized light microscope observing
To fan-shaped texture, Fig. 1 (a) is seen, the hexagonal phase texture with document report[27,33]It is similar, and the texture and Triton X-100/H2O
(50wt%:50wt%) texture (Fig. 2 (b)) is basically identical.And SAXS (curve a, Fig. 3) dispersion factor (q) ratio of predose
It is worth and isMatch with hexagonal phase (100), (110), (200) crystal face[27], show incorporation AUC liquid crystalline phase still
It is hexagonal phase structure.And mix the 40wt%Triton X-100 hexagonal phases liquid crystal texture (Fig. 2 (a) and Fig. 4) before and after AUC
Similar, AUC addition does not change phase.
According to phasor, 60wt%Triton X-100 systems are located at the phase boundray region of hexagonal phase and micelle volume.Incorporation
After AUC, its optical texture becomes fan-shaped texture (Fig. 1 (c)) by bar-shaped (Fig. 2 (c)), suggests the formation of hexagonal phase liquid crystal knot
Structure.And there is cross flower-shape texture (Fig. 1 (d)) behind 70wt%Triton X-100 regions, incorporation AUC, show there is stratiform liquid
Crystalline substance is formed[34,35].Based on result above as can be seen that AUC addition causes liquid crystalline phase region to broaden.Celik and Dag[36]Report
C12H25(OCH2CH2)10OH polyoxyethylene chain can pass through interaction of hydrogen bond with the hydrate of transition metal ions.Cause
This, it is probably polyoxyethylene chain and hydration UO that liquid crystal region, which broadens,2 2+The result of effect.
2.UO2The preparation of nano particle and sign
(a) and (b) is γ irradiation 50wt%Triton X-100 systems in Fig. 5, in 40Gymin-1Irradiate 300min systems
TEM and the SEM figure of standby obtained product.It can be seen that product particle size is in 60-80nm.Granule boundary part is relatively middle
Color is deep (Fig. 5 (a)).The TEM image (Fig. 5 (c)) of bigger multiplication factor more clearly from shows this feature.This shows institute
It is hollow nano-sphere to obtain product, and its wall thickness is 10-20nm.SAED images in Fig. 5 (c) illustrations have four diffraction rings, respectively away from
From center 0.314,0.277,0.195 and 0.166nm, with UO2(111), (200), (220), the spacing of lattice of (311) crystal face
0.315th, 0.2733,0.1933,0.1647nm (JCPDS NO.41-1422) is consistent, and this shows that prepared product is polycrystalline
UO2.XRD spectra (curve a, Fig. 6) and Emission in Cubic UO2Standard spectrogram (JCPDS NO.41-1422) be consistent, further confirm institute
It is UO to obtain product2.And the diffraction maximum of its widthization shows that nanosphere is molecular by the smaller nanoparticle of particle diameter, this obtains TEM (figures
5 (c)) observed result confirmation.HRTEM (Fig. 5 (d)) measures the diameter about 3-5nm of nano-particle.
Analyzed based on more than, hollow UO has been made in we2Nanosphere.
3. the thermal stability analysis of product
We have further carried out product thermal stability analysis.By the abundant UO for washing and drying2Nano material is in air
In 300 DEG C heat treatment 3 hours.Fig. 7 is the TEM image of product after heat treatment.As seen from the figure, product is still hollow and received
Rice ball.And XRD spectra (curve b, Fig. 6) and Emission in Cubic UO2Standard spectrogram it is consistent.SAED images (illustration, Fig. 7) occur in that with
Emission in Cubic UO2(111), (200), (220), the diffraction ring that is consistent of (311) crystal face.Product prepared by above analysis shows according to
It is so hollow UO2Nanosphere.
4. the influence of close rate
In radiation chemistry, close rate is the important means for regulating and controlling nanoparticle size pattern.We fix total absorbent
Measure as 12kGy, the pattern of nano particle is regulated and controled by conditioning agent dose rate.In 200Gymin-1Lower irradiation 60min, it is prepared
Obtained nano particle is solid nanospheres (Fig. 8 (a)).When reduction close rate, we have obtained the nanometer with hollow-core construction
Ball (Fig. 5 (c), 8 (b) and 8 (c)), and with the reduction of close rate, the wall of hollow ball is progressively thinning.And when close rate is further
It is reduced to 12Gymin-1When, particle is changed into solid construction again, and cavity diminishes (Fig. 8 (d)).This shows that close rate is to nanometer
Particle shape looks have important regulating and controlling effect.Experimental result based on us, 40-70Gymin-1It can obtain with larger cavity
Hollow nano-sphere.
The influence of 5.Triton X-100 concentration
In order to further explore effect of the Triton X-100 hexagonal phases in hollow nano-sphere preparation.We explore not
Influence with TritonX-100 contents to nano particle pattern and size.We are by the system of different Triton X-100 contents
It is placed in 70Gymin-1Duct is irradiated, and resulting product is analyzed.Micelle volume is widely used in the system of nano material
It is standby[37,38], based on this, we explore 25wt%Triton X-100 micelle volumes, the flowing of 25wt%Triton X-100 systems
Property it is strong, confirm that the hydrodynamic radius for obtaining micella are 2nm (Figure 10) by dynamic scattering analysis.It is prepared into the system
To solid nanometer UO2Particle (Fig. 9 (a))；In high concentration 70wt%Triton X-100 systems, solid nanometer UO is also prepared2
Particle (Fig. 9 (d)).And in hexagonal phase liquid crystal region, the irradiation of 45 and 55wt%Triton X-100 systems obtains hollow UO2Receive
Rice ball (Fig. 9 (b) and (c)).Result above shows hexagonal phase liquid crystal region for hollow UO2The formation of nanosphere plays important make
With.
AOT/H2O layered liquid crystal systems are in high pressure CO2Micelle volume can be transformed under effect, spherical micelle is used as template
Prepare hollow titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions[25].And we are characterized by POM (Fig. 1 (a)) and SAXS (curve b, Fig. 3) and confirmed
Do not undergone phase transition after the irradiation of 50wt%Triton X-100 systems, simply its optical texture becomes broken.This shows in liquid crystal
Defect or discontinuity increase[39]。
6. study mechanism
Using the liquid crystal system of γ radiolysis aqueous phases, water can produce many active species, such as e through radiolysisaq -, H,
OH etc. (formula 1)[40]。
eaq -U (VI) can be restored to U (IV), U (IV) in the basic conditions with OH-Effect obtains U (OH)4, further
Dehydration obtains UO2Nano particle (formula 2).
And OH free radicals are acted on and are consumed with Triton X-100 alkoxy grps.In 10%Triton X-100 micellas
In system, OH free radicals are 6.4 × 10 with Triton X-100 alkoxy grps reaction rate constant9L·mol-1·s-1[40]Make
Obtain whole system and keep reduction atmosphere, be conducive to U (VI) reduction and prevent U (IV) from aoxidizing.
In UO2Or U (OH)4Nano-particle formation UO2During hollow nano-sphere, there is the process of two competitions：One
It is UO2Or U (OH)4The simple aggregation process of nano-particle；Another then contains absorption, aggregation of the nano-particle in palisade layer
The processes such as deformation, fracture with palisade layer (Figure 11).In high dose rate (such as 200Gymin-1) under the conditions of, the shape of nano-particle
It is very fast into speed, it is impossible to which that the polyoxyethylene chain for being combined into the Triton X-100 of palisade layer is effectively captured, thus the process with
UO2Or U (OH)4Based on the simple aggregation process of nano-particle, solid UO is obtained2Nanosphere.When close rate is reduced,
Nano-particle synthesis speed reduces therewith, and nano-particle is attracted to fence layer surface by being acted on polyoxyethylene chain.Afterwards
The nano-particle of continuous generation is assembled using it as core so that uneven distribution of the nano-particle on palisade layer.Due to
TritonX-100 hexagonal liquid crystals can only exist at a temperature of less than 28 DEG C[32], the insufficient strength of its palisade layer is big.With receiving
The uneven accumulation of rice corpuscles, palisade layer is deformed upon, and final fracture, and Triton X-100 are wrapped in wherein, cause liquid
Crystal structure it is broken.In last handling process, Triton X-100 can be washed removing, so as to form hollow-core construction.Hollow ball
Wall thickness be probably due to the coefficient result of the two speed.When close rate is further decreased to 12Gymin-1When, due to
Nano-particle sedimentation rate is excessively slow, and substantial amounts of surfactant molecule is escaped, cause cavity to diminish so that final disappear and
Obtain solid UO2Nanosphere.
For 25wt% and 75wt%Triton X-100 micelle volumes, exist because its rigidity is not enough to support nano-particle
The absorption and aggregation on its surface, thus obtain solid nanoparticles.Therefore the rigidity of palisade layer is in hollow UO2The formation of nanosphere
During play an important role.
3rd, brief summary
Present invention experiment is prepared by the γ hexagonal phase liquid crystal systems for irradiating Triton X-100/AUC solution composition
By the molecular size of 1-10nm nanoparticles in 10-100nm, wall thickness 5-45nm hollow UO2Nanosphere.And find the product
It can be stabilized at 300 DEG C.Can be with the hollow knot of Effective Regulation particle by regulating and controlling close rate and Triton X-100 concentration
Structure and wall thickness, have important application prospect for research wall thickness regulation and control catalytic activity.Hollow UO2The formation mechenism of nanosphere can be with
It is divided into the processes such as absorption, aggregation, the deformation of palisade layer and fracture, the rigidity of liquid crystal system palisade layer is to hollow UO2Nanometer ball
There is regulating and controlling effect；Micelle volume can only obtain full particle.
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Claims (8)
1. a kind of hollow UO2The preparation method of nanosphere, comprises the following steps：
1) compound concentration >=2mmolL-1UO2(CO3)3 4-Alkaline solution；
2) in UO2(CO3)3 4-Triton X-100 are added in alkaline solution to be well mixed, and form hexagonal phase liquid crystal system；
3) under an inert atmosphere, to step 2) system close rate is carried out with gamma-rays or electron beam for 40~70Gymin-1's
Irradiation, obtains black precipitate, through centrifugation, washing, dries, obtains hollow UO2Nanosphere.
2. preparation method as claimed in claim 1, it is characterised in that step 1) UO for preparing2(CO3)3 4-The pH of alkaline solution
>=8, wherein UO2(CO3)3 4-Concentration be 2~20mmolL-1。
3. preparation method as claimed in claim 1, it is characterised in that step 1) described in UO2(CO3)3 4-Alkaline solution be by
Ammonium uranyl tricarbonate and alkaline matter mixed preparing are formed.
4. preparation method as claimed in claim 3, it is characterised in that the ammonium uranyl tricarbonate is converted from uranium raw material
Arrive, the uranium raw material is the raw material containing U (VI), passes through NH3And CO2Double gas lead to method or add (NH4)2CO3And NH4HCO3Legal system
It is standby to obtain ammonium uranyl tricarbonate.
5. preparation method as claimed in claim 1, it is characterised in that step 2) Triton X-100 are added into UO2(CO3)3 4-
After in alkaline solution, heating stirring is well mixed, and is then centrifuged for removing bubble, wherein Triton X-100 contents 35~
65wt%.
6. preparation method as claimed in claim 1, it is characterised in that step 3) irradiation dose be 4~50kGy.
7. preparation method as claimed in claim 1, it is characterised in that step 3) use 40~70Gymin-1Close rate spoke
According to 50~1250min.
8. preparation method as claimed in claim 1, it is characterised in that step 1) prepare containing 2~20mmolL-1Thricarbonate uranium
Acyl ammonium, 6~60mmolL-1Na2CO3Solution；Step 2) add certain mass Triton X-100, solution is moved into spoke
In looking after, 40 DEG C are heated to, magnetic agitation is well mixed, are then centrifuged for removing bubble；Step 3) N is led to irradiation tube2At one section
Between after tube sealing, with 40~70Gymin-1Close rate irradiate 50~1250min, obtain black UO2Precipitation.
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|---|---|---|---|---|
| US3270098A (en) * | 1965-03-08 | 1966-08-30 | Harold N Barr | Method of making hollow, spherical uo2 particles |
| CN103936076A (en) * | 2014-01-16 | 2014-07-23 | 中国科学院高能物理研究所 | Uranium oxide micro-sphere and preparation method thereof |
| CN105668640A (en) * | 2016-02-01 | 2016-06-15 | 北京大学 | Method for preparing ceramic-grade UO2 nuclear fuel |
| CN106044859A (en) * | 2016-05-30 | 2016-10-26 | 北京大学 | Method for preparing hollow UO2 nanospheres by ammonium uranyl carbonate solution irradiation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3270098A (en) * | 1965-03-08 | 1966-08-30 | Harold N Barr | Method of making hollow, spherical uo2 particles |
| CN103936076A (en) * | 2014-01-16 | 2014-07-23 | 中国科学院高能物理研究所 | Uranium oxide micro-sphere and preparation method thereof |
| CN105668640A (en) * | 2016-02-01 | 2016-06-15 | 北京大学 | Method for preparing ceramic-grade UO2 nuclear fuel |
| CN106044859A (en) * | 2016-05-30 | 2016-10-26 | 北京大学 | Method for preparing hollow UO2 nanospheres by ammonium uranyl carbonate solution irradiation |
Non-Patent Citations (1)
| Title |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU199744U1 (en) * | 2020-03-06 | 2020-09-17 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Device for producing uranium and plutonium oxides |
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