CN104973615B - Microwave burning preparation method of nano gadolinium oxide powder - Google Patents
Microwave burning preparation method of nano gadolinium oxide powder Download PDFInfo
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- CN104973615B CN104973615B CN201510364481.9A CN201510364481A CN104973615B CN 104973615 B CN104973615 B CN 104973615B CN 201510364481 A CN201510364481 A CN 201510364481A CN 104973615 B CN104973615 B CN 104973615B
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Abstract
The invention relates to a microwave burning preparation method of nano gadolinium oxide powder. The preparation method comprises the following steps: (1) mixing gadolinium oxide powder with a nitric acid solution to prepare a gadolinium nitrate solution; (2) evenly mixing the gadolinium nitrate solution with a critic acid solution according to a mole ratio of Gd3+ to citric acid of 4:(1-2) to obtain a precursor solution; (3) adjusting the pH value of the precursor solution to 8-10; (4) burning the precursor solution with an adjusted pH value by microwaves to obtain white powder; (5) burning the white powder for 2 to 5 hours at a constant temperature of 450 to 800 DEG C; (6) ball-grinding the burned white powder, and drying to obtain the target product. The preparation method adopts a microwave burning synthesis method, the microwave energy is utilized to vibrate the inner molecules in the precursor so as to generate heat, and the heat energy is evenly distributed.
Description
(1) technical field
The present invention relates to a kind of nanoscale gadolinium raw powder's production technology, belong to field of material preparation.
(2) background technology
The preparation of nano-ceramic powder is the matter of utmost importance of nano ceramic material and other relevant nanometer material industries, mainly makes
Preparation Method has solid phase method, liquid phase method and vapor phase method.Since the nineties in 20th century, nano-ceramic powder enters industrialization development
Stage.China mainly uses wet chemistry method and vapour deposition process to carry out the preparation of industrialized nano ceramic powder at present, mainly produces
Product include CaCO3、ZnO、Al2O3、SiOx、TiO2、Si3N4With SiC etc..
Nano oxidized gadolinium powder body can be used for various fluorescent material, the neutron absorber material in atomic pile, magnetic bubble material, sensitizing
Screen material.Also certain application is had, it is possible to as Gd-Ga garnet material at the aspect such as optical glass, electronics industry.
For the synthesis of nano oxidized gadolinium powder body, currently used commonplace method is sol-gal process, chemical precipitation method.
" synthesis of electrically conductive polyaniline micro-nano Gadolinia. composite and sign " Lixia ZHANGs etc., Guangxi Teachers College's journal is (natural
Science version), 2007,66-68, use chemical precipitation method to prepare the Gadolinia. flaky powder of micro/nano level, but prepare
Powder body is easily reunited, and uses ethanol as dispersant, and dispersion effect is more effective than Polyethylene Glycol, but the Gadolinia. size obtained is relatively
Greatly, 50～about 800nm；Using Polyethylene Glycol as dispersant, dispersion effect is poorer than ethanol, and Gadolinia. size is relatively
Little, but still at about 200nm." preparation of nano oxidized gadolinium/NBR composite and shielding properties research thereof " Zhao Yongfeng
Deng, rubber industry, 2010,581-585, use coprecipitation and spray drying method to combine to have prepared through high-temperature calcination and receive
Meter level Gadolinia., but preparation process duration comparatively speaking, technique is relatively cumbersome.
(3) summary of the invention
For the deficiencies in the prior art, the shortcoming that especially synthesis of Gadolinia. powder body is relatively costly, the present invention provides a kind of microwave
The method of conbustion synthesis nano oxidized gadolinium powder body.
Technical scheme is as follows:
The microwave burning preparation method of a kind of nano oxidized gadolinium powder body, comprises the following steps that
(1) configuration Gadolinium trinitrate solution: mixed with salpeter solution by Gadolinia. powder body, prepares Gadolinium trinitrate solution；Described oxidation
Gadolinium: the mol ratio of nitric acid is 1:(5-9)；
(2) Gadolinium trinitrate solution mixes with citric acid: by Gadolinium trinitrate solution with citric acid solution by Gd3+: citric acid mol ratio
For 4:(1-2) mix homogeneously, prepare precursor solution；
(3) regulation pH value: the pH value of precursor solution is adjusted to 8～10；
(4) microwave burning synthesis: by the precursor solution microwave burning synthesis after regulation pH value, prepare white powder；
(5) calcining: by white powder 450 DEG C～800 DEG C insulation calcining 2-5h in Muffle furnace；
(6) ball milling: by the material ball milling after calcining, is dried, i.e. prepares nano oxidized gadolinium powder body.
According to the invention it is preferred to, the Gadolinia. described in step (1): the mol ratio of nitric acid is 1:(6-7), enter one
Preferably, the concentration of described salpeter solution is 30-40wt% to step, and salpeter solution usable concentration is the concentrated nitric acid of 65～69wt%
Obtain with deionized water dilution.
According to the invention it is preferred to, the citric acid described in step (2) is monohydrate potassium (C6H8O7·H2O),
Gd3+: C6H8O7·H2The mol ratio of O is 4:(1-1.5).
According to the invention it is preferred to, step regulates pH with ammonia in (3).
According to the invention it is preferred to, described in step (4), the equipment of microwave burning is microwave oven.Before during microwave burning
Driving moisture in liquid solution to be evaporated, solute reacts.The temperature of microwave oven is set to middle temperature or middle high temperature, and the response time is
40min～60min, depending on response time visual response thing amount, moisture is evaporated rear pulverulent product and is changed into white powder by yellow is cellular
Powder.
According to the invention it is preferred to, in step (5), the equipment of calcining is Muffle furnace, and Muffle furnace calcining programming rate is
5～10 DEG C/min；It is further preferred that described calcining heat is 500 DEG C～800 DEG C.By calcining further, make in powder body
Unnecessary C, N element voloxidation, thus purify powder body, meanwhile make powder body crystallize further obtain more complete brilliant
Grain.
According to the invention it is preferred to, in step (6), ball milling uses wet ball grinding, and wet ball grinding uses ethanol to be situated between for dispersion
Matter, employing polyvinylpyrrolidone is dispersant.
The principle of the present invention:
The present invention uses nitric acid, Gadolinia., citric acid, ammonia etc. as raw material, and household microwave oven can be used as reaction
Stove, uses chemical method to synthesize the precursor solution of nano oxidized gadolinium, precursor solution is placed in household microwave oven combustion afterwards
Burning, depending on precursor solution volume, be evaporated by moisture in precursor solution burning time, solute reacts.Burning is closed
Cheng Hou, dissolves powder body ethanol and adds polyvinylpyrrolidone as dispersant, and batch mixing is dried, ground by lapping using star lapping machine
Being nano oxidized gadolinium powder body after mill, particle diameter is 50～100nm.
The present invention uses microwave combusion method, and microwave has certain catalytic action to chemical reaction；The heat transfer theory of microwave heating is not
Being same as traditional heat transfer theory and HEAT TRANSFER LAW, microwave has certain penetration to material, and being energized material is to inhale ripple thing
The molecule of matter produces the direct heat release of thermal vibration, and therefore, heated material is heated highly uniform；Microwave energy supply is not because of thermal source or sends out
Hot material and bring any secondary pollution into heated material.Presoma of the present invention preparation adds citric acid and participates in reaction, fill
Dividing the superiority utilizing organic-inorganic material hybridization to react, citric acid can ionize out 3 H as a kind of stronger organic acid+,
Can be with Gd in Gadolinium trinitrate solution3+Hydridization, here with the frame structure of citric acid molecule, during making microwave burning, vibration is produced
Heat is more uniform, and powder granule is difficult to reunite, and does not bring the impurity element of difficult removal into simultaneously.In addition for promoting that reaction makes
Promote that reaction is carried out with ammonia as catalyst, intuitively show as regulating pH value.For promoting powder body crystallization, the most carefully
Changing crystal grain, find equilibrium point between the easy cluster of nano-powder and the too high crystal grain of calcining heat are grown up, the present invention determines after probing into
Calcining heat is optimal at 450 DEG C～800 DEG C.In calcination process, the element such as C, N in powder body can make nanometer with voloxidation
Gadolinia. powder body is purified.
(4) beneficial effect:
(1) present invention uses microwave combustion synthesizing method, utilizes microwave energy, makes presoma be vibrated heat production by interior molecules, heat
Amount is evenly distributed.
(2) present invention uses Organic substance citric acid to participate in reaction, and Gadolinium trinitrate generation organic inorganic hybridization, as a kind of stronger
Organic acid, 1mol citric acid ionizable go out 3molH+, Gd under ionic bond effect3+May replace H+, thus make with citric acid
For medium, form organic inorganic hybrid.
(3) the nano oxidized gadolinium diameter of particle of present invention synthesis is between 50～100nm, the powder prepared relative to additive method
Body granularity is less and is uniformly dispersed.
(5) accompanying drawing explanation
Fig. 1 is the SEM figure of the low enlargement ratio of Gadolinia. powder body that the embodiment of the present invention 1 prepares；
Fig. 2 is the SEM figure of the Gadolinia. powder body high magnification that the embodiment of the present invention 1 prepares；
Fig. 3 is the XRD figure of the Gadolinia. powder body that the embodiment of the present invention 1 prepares.
(6) detailed description of the invention
Below in conjunction with embodiment, technical scheme is described further, but institute of the present invention protection domain is not limited to this.
The raw materials used convenient source that is, commercial products in embodiment.
Embodiment 1:
The microwave burning preparation method of a kind of nano oxidized gadolinium powder body, comprises the following steps that
(1) configuration Gd (NO3)3Solution: weigh 20g micron order Gadolinia. powder body, by mass fraction 69% concentrated nitric acid
31.2g 28.2g deionized water is diluted to 35wt%, Gd in molar ratio2O3:HNO3=1:6, configures Gd (NO3)3
Solution, is placed in solution in 500ml beaker and dissolves in magnetic stirrer, ultrasonic disperse 5min；
(2) Gadolinium trinitrate solution mixes with citric acid: weighs 92.4g monohydrate potassium and is dissolved in 150ml water, by mole
Compare Gd3+: C6H8O7·H2O=4:1 configures precursor solution, is placed in 50 DEG C of constant temperature water baths, magnetic agitation
10min；
(3) regulation pH value: dripping ammonia regulation pH value in precursor solution is 8；
(4) microwave burning synthesis: precursor solution is placed in conbustion synthesis in household microwave oven, uses moderate heat, and the time is about
30min, goods are changed into white powder by yellow is cellular；
(5) Muffle furnace calcining: be placed in Muffle furnace by white powder, be warming up to 500 DEG C in 50min, is incubated 3h, removes
The elements such as C, N excessive in powder body, with CO2、N2O4Form remove；
(6) planetary ball mill: use 300ml dehydrated alcohol as disperse medium, by the material planetary ball mill 2h after calcining,
12h is dried, it is thus achieved that Gadolinia. nano-powder in 80 DEG C of vacuum drying oven.
The Gadolinia. nano-powder that the present embodiment obtains as shown in Figure 1, 2, from Fig. 1,2, Gadolinia. nano-powder grain
Footpath is 50～100nm, is evenly distributed.
Embodiment 2:
The microwave burning preparation method of a kind of nano oxidized gadolinium powder body, comprises the following steps that
(1) configuration Gd (NO3)3Solution: weigh 20g micron order Gadolinia. powder body, the dense nitre of 36.6g mass fraction 68%
Concentrated nitric acid is diluted to 35wt% by acid 32.9g deionized water, Gd in molar ratio2O3:HNO3=1:7 configures Gd
(NO3)3Solution, is placed in solution 500ml beaker and dissolves in magnetic stirrer, ultrasonic disperse 5min；
(2) Gadolinium trinitrate solution mixes with citric acid: weighs 92.4g monohydrate potassium and is dissolved in 150ml water, by mole
Compare Gd3+: C6H8O7·H2O=4:1 configures precursor solution, is placed in 50 DEG C of constant temperature water baths, magnetic agitation
10min；
(3) regulation pH value: dripping ammonia regulation pH value in precursor solution is 10；
(4) microwave burning synthesis: precursor solution is placed in conbustion synthesis in household microwave oven, uses moderate heat, and the time is about
30min, goods are changed into white powder by yellow is cellular；
(5) Muffle furnace calcining: be placed in Muffle furnace by white powder, be warming up to 500 DEG C in 50min, is incubated 3h, removes
The elements such as C, N excessive in powder body, with CO2、N2O4Form remove；
(6) planetary ball mill: using 300ml dehydrated alcohol as disperse medium, polyvinylpyrrolidone, will as dispersant
Material planetary mills 2h after calcining, dries 12h in 80 DEG C of vacuum drying oven, it is thus achieved that Gadolinia. nano-powder.
Embodiment 3:
The microwave burning preparation method of a kind of nano oxidized gadolinium powder body, comprises the following steps that
(1) configuration Gd (NO3)3Solution: weigh 20g micron order Gadolinia. powder body, the dense nitre of 36.6g mass fraction 68%
Concentrated nitric acid is diluted to 35wt% by acid 28.2g deionized water, Gd in molar ratio2O3:HNO3=1:8 configures Gd
(NO3)3Solution, is placed in solution 500ml beaker and dissolves in magnetic stirrer, ultrasonic disperse 5min；
(2) Gadolinium trinitrate solution mixes with citric acid: weighs 92.4g monohydrate potassium and is dissolved in 150ml, in molar ratio
Gd3+: C6H8O7·H2O=4:1.5 configures precursor solution, is placed in 50 DEG C of constant temperature water baths, magnetic agitation 10min；
(3) regulation pH value: dripping ammonia regulation pH value in precursor solution is 9；
(4) microwave burning synthesis: precursor solution is placed in conbustion synthesis in household microwave oven, uses moderate heat, and the time is about
30min, goods are changed into white powder by yellow is cellular；
(5) Muffle furnace calcining: be placed in Muffle furnace by white powder, be warming up to 800 DEG C in 50min, is incubated 2h, goes gumming
The elements such as C, N excessive in body, with CO2、N2O4Form remove；
(6) planetary ball mill: using 300ml dehydrated alcohol as disperse medium, polyvinylpyrrolidone, will as dispersant
Material planetary mills 2h after calcining, dries 12h in 80 DEG C of vacuum drying oven, it is thus achieved that Gadolinia. nano-powder.
Embodiment 4:
The microwave burning preparation method of a kind of nano oxidized gadolinium powder body, comprises the following steps that
(1) configuration Gd (NO3)3Solution: weigh 20g micron order Gadolinia. powder body, the dense nitre of 36.6g mass fraction 68%
Acid 32.9g deionized water is diluted to 35wt%, Gd in molar ratio2O3:HNO3=1:9 configures Gd (NO3)3Molten
Liquid, is placed in 500ml beaker and dissolves in magnetic stirrer, ultrasonic disperse 5min；
(2) Gadolinium trinitrate solution mixes with citric acid: weighs 92.4g monohydrate potassium and is dissolved in 150ml water, by mole
Compare Gd3+: C6H8O7·H2O=4:2 configures precursor solution, is placed in 50 DEG C of constant temperature water baths, magnetic agitation 10min；
(3) regulation pH value: dripping ammonia regulation pH value in precursor solution is 10；
(4) microwave burning synthesis: precursor solution is placed in conbustion synthesis in household microwave oven, uses moderate heat, and the time is about
30min, goods are changed into white powder by yellow is cellular；
(5) Muffle furnace calcining: be placed in Muffle furnace by white powder, be warming up to 600 DEG C in 50min, is incubated 2h, goes gumming
The elements such as C, N excessive in body, with CO2、N2O4Form remove；
(6) planetary ball mill: using 300ml dehydrated alcohol as disperse medium, polyvinylpyrrolidone, will as dispersant
Material planetary mills 2h after calcining, dries 12h in 80 DEG C of vacuum drying oven, it is thus achieved that Gadolinia. nano-powder.
Comparative example 1:
As described in Example 1, step (4) microwave burning is not the most used to synthesize, dinectly bruning after regulation pH.
The Gadolinia. nano-powder obtained after dinectly bruning is because of inequality of being heated, and distribution of particles is uneven.Owing to reaction is excessively acute
Strong, the element easy direct oxidation volatilization such as C, N is reacted with oxygen element in solution, and Cd3+Can not get pairing O2+Simultaneously no
To reduction, so reaction is not exclusively, poor effect.
Comparative example 2:
As described in Example 1, except for the difference that step (3) does not regulate pH value.
The Gadolinia. nano-powder crystal grain obtained becomes big, and manufacturing cycle is elongated.Under conditions of not having catalyst, presoma is molten
Liquid is during microwave burning, and the response time is elongated, after preparing white forerunner's solid mixture, through the powder of Muffle furnace calcining
End has a large amount of black C powder residue, need to calcine except C further.Crystal grain burning is the most easily made after increasing reaction time
And grow up.
Claims (9)
1. a microwave burning preparation method for nano oxidized gadolinium powder body, comprises the following steps that
(1) configuration Gadolinium trinitrate solution: mixed with salpeter solution by Gadolinia. powder body, prepares Gadolinium trinitrate solution；Described Gadolinia.: nitre
The mol ratio of acid is 1:(5-9)；
(2) Gadolinium trinitrate solution mixes with citric acid: by Gadolinium trinitrate solution with citric acid solution by Gd3+: citric acid mol ratio is
4:(1-2) mix homogeneously, prepares precursor solution；
(3) regulation pH value: the pH value ammonia of precursor solution is adjusted to 8 ~ 10；
(4) microwave burning synthesis: by the precursor solution microwave burning synthesis after regulation pH value, obtain white powder；
(5) calcining: by white powder in 450 DEG C ~ 800 DEG C insulation calcining 2-5h；
(6) ball milling: by the material ball milling after calcining, is dried, i.e. prepares nano oxidized gadolinium powder.
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (1)
Described in Gadolinia.: the mol ratio of nitric acid is 1:(6-7).
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (1)
Described in the concentration of salpeter solution be 30-40wt%.
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (2)
Described in citric acid be monohydrate potassium (C6H8O7·H2O), Gd3+: C6H8O7·H2The mol ratio of O is 4:(1-1.5).
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (4)
Described in the equipment of microwave burning be microwave oven.
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (5)
The equipment of middle calcining is Muffle furnace, and Muffle furnace calcining programming rate is 5 ~ 10 DEG C/min.
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (5)
Described in calcining heat be 500 DEG C ~ 800 DEG C.
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 1, it is characterised in that step (6)
Middle ball milling uses wet ball grinding.
The microwave burning preparation method of nano oxidized gadolinium powder body the most according to claim 8, it is characterised in that step (6)
Middle wet ball grinding uses ethanol to be disperse medium, and employing polyvinylpyrrolidone is dispersant.
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| CN108483480A (en) * | 2018-04-11 | 2018-09-04 | 内蒙古科技大学 | The method for preparing gadolinium oxide with plant precipitating reagent |
| CN109231254B (en) * | 2018-11-20 | 2020-06-16 | 常州市卓群纳米新材料有限公司 | Preparation method of high-purity high-dispersion gadolinium oxide particles with D50 particle size of 0.4-0.6 micrometer |
| CN109399689B (en) * | 2018-12-17 | 2021-08-17 | 中铝广西国盛稀土开发有限公司 | Method for preparing rare earth oxide by microwave technology |
| CN111018527A (en) * | 2019-12-26 | 2020-04-17 | 江西鑫泰功能材料科技有限公司 | Preparation method of nano gadolinium oxide for dielectric ceramic capacitor |
| CN111533157A (en) * | 2020-04-24 | 2020-08-14 | 广西科学院 | Microwave calcination preparation method of gadolinium oxide nano powder |
| CN111533158A (en) * | 2020-04-24 | 2020-08-14 | 广西科学院 | Microwave calcination preparation method of dysprosium oxide nano powder |
| CN111634935A (en) * | 2020-04-24 | 2020-09-08 | 广西科学院 | Microwave preparation method of nano rare earth oxide |
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