CN102701273B - Preparation method of nano dysprosium titanate powder - Google Patents
Preparation method of nano dysprosium titanate powder Download PDFInfo
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- CN102701273B CN102701273B CN 201210160158 CN201210160158A CN102701273B CN 102701273 B CN102701273 B CN 102701273B CN 201210160158 CN201210160158 CN 201210160158 CN 201210160158 A CN201210160158 A CN 201210160158A CN 102701273 B CN102701273 B CN 102701273B
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Abstract
The invention relates to a preparation method of nano dysprosium titanate powder. The method comprises the steps of dropping alcohol/water/glacial acetic acid mixed solution containing dysprosium nitrate into titanium acid butyl ester alcohol solution according to the molar ratio of Dy:Ti=(1-2:1); ageing obtained colloidal sol at the room temperature so as to obtain gel; drying and crushing the gel, arranging the gel into an aluminum oxide crucible, sintering the gel at 8001100 DEG C so as to obtain the nano dysprosium titanate powder. The nano dysprosium titanate powder preparation process is simple, the grain size of the powder is even and small, and the purity is high; and the powder can be used as neutron absorbing materials.
Description
Technical field
The present invention relates to a kind of preparation method who is used as the nano barium titanate dysprosium powder of neutron absorber material, belong to the neutron absorber material technical field.
Background technology
The Main Function of Shielding Materials for Nuclear Radiation is absorption or weakens neutron and gamma-rays.In nuclear reactor, be thermal neutron or epithermal neutrons by slowing down through the neutron major part behind pressure vessel and the gas-tight silo, this type of neutron needs the larger material of thermal neutron absorption cross section effectively to absorb and is unlikely to overflow.
The B10 isotropic substance has very large thermal neutron absorption cross section, thus in nuclear industry norbide and boron steel is used in the control rod and as shielding material.But, owing to B when radiation
10(n, the α) reaction that occurs so that " expansion " appears in these materials behind irradiation, forms nuclear vacuole.For boron carbide ceramics, irradiation " expansion " can cause the inefficacy of covering.Therefore, in the work-ing life of absorbing material, be decided by to a great extent the irradiation stability of material rather than the decline of neutron-absorbing efficient.In view of more than, wish to utilize (n, α) reaction to occur and the alternative boron materials of stupalith such as the dysprosium of absorption thermal neutron, europium, samarium, gadolinium, hafnium base.The irradiation experiment of pottery absorbing material shows that fluorite type lanthanide oxide base pottery presents best Antiradiation injury.In these materials, the metatitanic acid dysprosium once was used in Muscovite water-water power reactor 15 years [referring to Amit Sinha and Beant Prakash Sharma.Development of Dysprosium Titanate Based Ceramics, J.Am.Ceram.Soc., 88[4] 1064 – 1066 (2005)].Metatitanic acid dysprosium pottery as neutron absorber material except high neutron-absorbing efficient, do not have very large swelling, under neutron radiation, do not exit, high-melting-point (~ 1870 ° of C) and more than 1000 ℃ not with the coating effect etc., can be with ball ball or particulate state as control rod.
V.D.Risovany etc. are with Dy
2O
3, TiO
2Be raw material, the an amount of metal molybdenum of admixture, metatitanic acid dysprosium powder has been synthesized in high-temperature calcination, referring to V.D.Risovany, E.E.Varlashova, D.N.Suslov.Dysprosium titanate as an absorber material for control rods.Journal ofNuclear Materials, 281 (2000) 84-89; The people such as Amit Sinha are also with Dy
2O
3, TiO
2Be raw material, by adding an amount of molybdenum oxide as stablizer, obtained metatitanic acid dysprosium powder in 4 hours 1600 ℃ of lower calcinings, mean particle size is more than 5 μ m, referring to Amit Sinha and Beant Prakash Sharma.Development of Dysprosium Titanate Based Ceramics, J.Am.Ceram.Soc., 88[4] 1064 – 1066 (2005).Adopt the solid phase method reaction method can synthesize metatitanic acid dysprosium powder, but with respect to chemical process, the particle diameter of synthetic powder is large, mixes easily impurity.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method for preparing high purity, evengranular nano barium titanate dysprosium powder.
Technical scheme of the present invention is as follows:
A kind of preparation method of nano barium titanate dysprosium powder, step is as follows:
(1) butyl (tetra) titanate is under agitation joined in the dehydrated alcohol, the volume ratio of butyl (tetra) titanate and dehydrated alcohol is 0.5 ~ 3:1, gets the butyl (tetra) titanate alcoholic solution;
(2) it is even dehydrated alcohol to be joined deionized water for stirring, dehydrated alcohol and deionized water volume ratio 3:(1～2), get alcohol solution, add the salt acid for adjusting pH 0 ~ 3; Add Glacial acetic acid and Dysprosium trinitrate, stirring is dissolved it fully, makes the mixing solutions that Dysprosium trinitrate content is 40-65wt%; The dosage of Glacial acetic acid is the 3-13wt% of Dysprosium trinitrate weight;
(3) Dy:Ti=1 ~ 2:1 in molar ratio is added drop-wise to the mixing solutions that contains Dysprosium trinitrate of step (2) in the butyl (tetra) titanate alcoholic solution of step (1), fully stirs, and gets mixed sols;
(4) mixed sols that step (3) is made is ageing 20～30h at room temperature, obtains gel; Then gel is dry under 50～80 ℃, pulverize, cross 100～200 mesh sieves, obtain metatitanic acid dysprosium presoma xerogel powder;
(5) metatitanic acid dysprosium presoma xerogel is packed in the alumina crucible, at 800～1100 ℃ temperature lower calcination, insulation 0.5 ~ 2h obtains nano barium titanate dysprosium powder.
Preferably, the volume ratio of the butyl (tetra) titanate of described step (1) and dehydrated alcohol is 1 ~ 2.5:1;
In the described step (2), preferred dehydrated alcohol and deionized water volume ratio 3:(1～1.5), pH=0 ~ 2, mol ratio Dy:Ti is 1 ~ 1.2:1; The metering specific energy of strict control dysprosium and titanium improves product purity well.
Preferably, the calcining temperature of described step (5) is incubated 1 ~ 2h at 850 ~ 1000 ℃.
But the raw material among the present invention is all buied in market, and wherein Dysprosium trinitrate can directly be bought the commercially available prod, also can make the Dysprosium trinitrate powder by dysprosium oxide and nitric acid reaction, drying by prior art.
Nano barium titanate dysprosium powder of the present invention is take Dysprosium trinitrate and butyl (tetra) titanate as raw material, adopts chemical sol-gel technology to prepare metatitanic acid dysprosium presoma xerogel, and then high-temperature calcination is prepared from alumina ceramic crucible; The present invention in Dysprosium trinitrate solution, add an amount of Glacial acetic acid when being added drop-wise in the Dysprosium trinitrate solution to slow down butyl (tetra) titanate solution butyl (tetra) titanate hydrolysis with speed polymerization.The method technique is simple, combines sol gel process and can prepare the advantages such as the less and size distribution of powder crystal grain is even, has synthesized metatitanic acid dysprosium nano-powder under relatively low temperature.Compare with solid reaction process and the invention has the advantages that:
1. the raw material of the synthetic metatitanic acid dysprosium use of the present invention is easy to get, and mild condition does not increase raw material and process costs;
In the synthetic metatitanic acid dysprosium process of the present invention the element metering of dysprosium and titanium than can strictly controlling the product purity height;
3. the synthetic metatitanic acid dysprosium powder crystallization formation temperature of the present invention is lower;
4. the metatitanic acid dysprosium powder granularity prepared of the present invention is even, and particle diameter is at the nano level yardstick;
The nano barium titanate dysprosium powder of the present invention's preparation can be used for preparing the metatitanic acid dysprosium neutron absorber material of fine crystalline structure, can be used as the stupalith of command bundle rods for nuclear reactors, regulating rod, emergency rod, safety rod, shielding rod.
Description of drawings
Fig. 1 is the SEM figure of the metatitanic acid dysprosium powder of embodiment 3 preparations.
Fig. 2 is the XRD figure of the metatitanic acid dysprosium powder of embodiment 3 preparations.
Embodiment
The invention will be further described below in conjunction with embodiment, but be not limited to this.
Embodiment 1: mol ratio Dy:Ti=1:1
1, the 40ml butyl (tetra) titanate is joined in the 20ml dehydrated alcohol when stirring, get the butyl (tetra) titanate alcoholic solution;
2, it is even the 30ml dehydrated alcohol to be joined the 10ml deionized water for stirring, and adding the salt acid for adjusting pH is 2; Add the 4ml Glacial acetic acid to slow down the speed of butyl (tetra) titanate hydrolysis and polymerization, then add the 41g Dysprosium trinitrate in solution, stirring is dissolved it fully, gets Dysprosium trinitrate solution;
3, the Dysprosium trinitrate solution with step 2 slowly is added drop-wise in the broad liquid of butyl (tetra) titanate of step 1, fully stirs, and gets mixed sols;
4, the mixed sols that step 3 is made is ageing 24h at room temperature, obtains gel; Then gel is dry under 80 ℃, pulverize, cross 100 mesh sieves, obtain metatitanic acid dysprosium presoma xerogel powder;
5, metatitanic acid dysprosium presoma xerogel is packed in the alumina crucible, put into retort furnace, pressureless sintering under 900 ℃ temperature, insulation 1h obtains 48g metatitanic acid dysprosium nanopowder.
The granularity of the metatitanic acid dysprosium powder that obtains is about 80nm, and purity is more than 97%, and yield is about 90%.
Embodiment 2: mol ratio Dy: Ti=1.7:1
1, the 40ml butyl (tetra) titanate is joined in the 40ml dehydrated alcohol when stirring, get butyl (tetra) titanate solution;
2, it is even the 30ml dehydrated alcohol to be joined the 20ml deionized water for stirring, and adding the salt acid for adjusting pH is 1.5; Add the 2ml Glacial acetic acid to slow down the speed of butyl (tetra) titanate hydrolysis and polymerization, Dy:Ti is 1.7:1 in molar ratio, adds the 69.7g Dysprosium trinitrate in solution, stirs it is dissolved fully, gets Dysprosium trinitrate solution;
3, the Dysprosium trinitrate solution with step 2 slowly is added drop-wise in the broad liquid of butyl (tetra) titanate of step 1, fully stirs, and gets mixed sols;
4, the mixed sols that step 3 is made is ageing 24h at room temperature, obtains gel; Then gel is dry under 50 ℃, pulverize, cross 200 mesh sieves, obtain metatitanic acid dysprosium presoma xerogel powder;
5, metatitanic acid dysprosium presoma xerogel is packed in the alumina crucible, be put into pressureless sintering in the sintering oven, 5 ℃/min of heat-up rate, top temperature is 900 ℃, insulation 1h, take argon gas as protective gas, naturally cooling obtains 42g metatitanic acid dysprosium nanopowder.
The granularity of the metatitanic acid dysprosium powder that obtains is about 100nm, and purity is more than 87%, and yield is about 78%.
Embodiment 3: mol ratio Dy:Ti=1.2:1
1, the 40ml butyl (tetra) titanate is joined in the 20ml dehydrated alcohol when stirring, get butyl (tetra) titanate solution;
2, it is even the 20ml dehydrated alcohol to be joined the 10ml deionized water for stirring, and adding the salt acid for adjusting pH is 0.5～1; Add the 3ml Glacial acetic acid to slow down the speed of butyl (tetra) titanate hydrolysis and polymerization, Dy:Ti is 1.2:1 in molar ratio, adds the 49g Dysprosium trinitrate in solution, stirs it is dissolved fully, gets Dysprosium trinitrate solution;
3, the Dysprosium trinitrate solution with step 2 slowly is added drop-wise in the broad liquid of butyl (tetra) titanate of step 1, fully stirs, and gets mixed sols;
4, the mixed sols that step 3 is made is ageing 24h at room temperature, obtains gel; Then gel is dry under 70 ℃, pulverize, cross 100 mesh sieves, obtain metatitanic acid dysprosium presoma xerogel powder;
5, metatitanic acid dysprosium presoma xerogel is packed in the alumina crucible, discharge plasma sintering in the sintering oven of packing into, top temperature is 1000 ℃, insulation 0.5h, naturally cooling obtains 44g metatitanic acid dysprosium nanopowder.
The granularity of the metatitanic acid dysprosium powder that obtains is about 100nm, and purity is more than 95%, and yield is about 82%.
Claims (4)
1. the preparation method of a nano barium titanate dysprosium powder, step is as follows:
(1) butyl (tetra) titanate is under agitation joined in the dehydrated alcohol, the volume ratio of butyl (tetra) titanate and dehydrated alcohol is 0.5 ~ 3:1, gets the butyl (tetra) titanate alcoholic solution;
(2) it is even dehydrated alcohol to be joined deionized water for stirring, dehydrated alcohol and deionized water volume ratio 3:(1～2), get alcohol solution, add the salt acid for adjusting pH 0 ~ 3; Add Glacial acetic acid and Dysprosium trinitrate, stirring is dissolved it fully, makes the mixing solutions that Dysprosium trinitrate content is 40-65wt%; The dosage of Glacial acetic acid is the 3-13wt% of Dysprosium trinitrate weight;
(3) Dy:Ti=1 ~ 2:1 in molar ratio is added drop-wise to the mixing solutions that contains Dysprosium trinitrate of step (2) in the butyl (tetra) titanate alcoholic solution of step (1), fully stirs, and gets mixed sols;
(4) mixed sols that step (3) is made is ageing 20～30h at room temperature, obtains gel; Then gel is dry under 50～80 ℃, pulverize, cross 100～200 mesh sieves, obtain metatitanic acid dysprosium presoma xerogel powder;
(5) metatitanic acid dysprosium presoma xerogel is packed in the alumina crucible, at 800～1100 ℃ temperature lower calcination, insulation 0.5 ~ 2 h obtains nano barium titanate dysprosium powder.
2. the preparation method of nano barium titanate dysprosium powder as claimed in claim 1 is characterized in that the butyl (tetra) titanate of step (1) and the volume ratio of dehydrated alcohol are 1 ~ 2.5:1.
3. the preparation method of nano barium titanate dysprosium powder as claimed in claim 1 is characterized in that in the step (2), dehydrated alcohol and deionized water volume ratio 3:(1～1.5), pH=0 ~ 2; In the step (3), mol ratio Dy:Ti is 1 ~ 1.2:1.
4. the preparation method of nano barium titanate dysprosium powder as claimed in claim 1 is characterized in that the calcining temperature of step (5) at 850 ~ 1000 ℃, insulation 1 ~ 2 h.
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| CN104477977B (en) * | 2014-12-11 | 2016-05-11 | 山东大学 | The synthetic Dy of a kind of molten-salt growth method2TiO5The method of powder |
| CN105161144B (en) * | 2015-08-07 | 2017-09-08 | 厦门大学 | A kind of preparation method of nuclear reactor neutron absorber material metatitanic acid dysprosium pellet |
| CN107216142B (en) * | 2017-07-20 | 2019-10-25 | 陕西师范大学 | A kind of high thermal stability copper titanate cadmium X8R ceramic material |
| CN107188558B (en) * | 2017-07-20 | 2019-10-25 | 陕西师范大学 | A kind of alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density and preparation method thereof |
| CN107216147B (en) * | 2017-07-20 | 2019-10-25 | 陕西师范大学 | A kind of high breakdown field strength zirconia titanate copper cadmium giant dielectric ceramic material and preparation method thereof |
| CN108439462B (en) * | 2018-03-28 | 2020-09-22 | 新沂市东方硕华光学材料有限公司 | Preparation method of pyrochlore type rare earth titanate powder |
| CN113213916B (en) * | 2021-05-19 | 2022-02-11 | 山东大学 | Fluorite-structured dysprosium titanate reactor control rod and preparation method thereof |
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