CN108394926B - A kind of nano oxidized dysprosium raw powder's production technology - Google Patents
A kind of nano oxidized dysprosium raw powder's production technology Download PDFInfo
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- CN108394926B CN108394926B CN201810570450.2A CN201810570450A CN108394926B CN 108394926 B CN108394926 B CN 108394926B CN 201810570450 A CN201810570450 A CN 201810570450A CN 108394926 B CN108394926 B CN 108394926B
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- dysprosium
- nano oxidized
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of nano oxidized dysprosium raw powder's production technology, preparation process includes: 1) to prepare acid feed liquid containing dysprosium；2) alkaline mixed solution containing precipitating reagent and sorbate is prepared；3) acid feed liquid containing dysprosium is added dropwise in the alkaline mixed solution in ultrasonic field while stirring, forms reaction solution, controls the temperature of the reaction solution lower than 65 DEG C, until the pH of the reaction solution is 5-7, obtains sediment；4) sediment is calcined through the washing of volatile solvent, drying and two steps, obtains nano oxidized dysprosium powder.Such nano oxidized dysprosium diameter of particle is small, high degree of dispersion and reunites few.
Description
Technical field
The invention belongs to rare earth oxide material preparation field, in particular to a kind of preparation side of nano oxidized dysprosium powder
Method.
Background technique
Rare earth oxide is in magnetic material, catalysis material, hydrogen storage material, optical glass, optical fiber and ceramic condenser etc.
Field is widely used.Dysprosia has excellent physicochemical properties, when its particle size gradually decreases to nano-scale, than
Surface area increase generates skin effect, while having quantum size effect and macro quanta tunnel effect, becomes specific function material
Expect the basis of development.The grain diameter difficulty that mechanical grinding obtains in traditional preparation methods reaches nanoscale；And sol-gel method, water
The nano oxidized dysprosium that the wet-chemicals mode such as thermal method obtains often bad dispersibility, is easy to happen reunion.
In patent CN105502467A, nano oxidized dysprosium is prepared using the positive precipitation method, it need to be molten before precipitating reagent is added dropwise
Exhibiting high surface activating agent is added in liquid, it is unfriendly to environment, and remaining organic compound easily causes office during heating
Significantly reunite in portion.
In patent CN106315656A, using the nano oxidized dysprosium of graphene coated, thus the production for inhibiting nanoparticle to reunite
Raw, preparation method is complicated, with high costs, while the introducing of graphene limits the extensive use of dysprosia to a certain degree.
Summary of the invention
The present invention is intended to provide a kind of nano oxidized dysprosium raw powder's production technology, using reverse-precipitation, and by
Sorbate is added in precipitating reagent and is arranged in pairs or groups to the selection of the techniques such as concentration, the ultrasonic field technology of sorbate, and primary grain is obtained
Diameter is small, good dispersion, few nano oxidized dysprosium powder of reuniting.
The invention discloses a kind of nano oxidized dysprosium raw powder's production technologies, which comprises the following steps:
1) the acidity feed liquid containing dysprosium that pH is 2-3, the concentration of dysprosium chloride and/or dysprosium nitrate is 1.2mol/L-2mol/L is prepared；
2) alkaline mixed solution containing precipitating reagent and sorbate is prepared, the concentration of the precipitating reagent is 1.5mol/L-
2.5mol/L, the concentration of the sorbate are 0.012mol/L-0.2mol/L；
3) the acid feed liquid containing dysprosium is added dropwise in the alkaline mixed solution in ultrasonic field while stirring, forms reaction solution,
The temperature of the reaction solution is controlled lower than 65 DEG C, until the pH of the reaction solution is 5-7, obtains sediment；The speed of the stirring
For 10r/min-100r/min, the frequency of the ultrasonic field is 40kHz-80kHz；
4) sediment is calcined through the washing of volatile solvent, drying and two steps, obtains nano oxidized dysprosium powder.
The present invention uses reverse-precipitation, and is matched by the collaboration of the techniques such as the concentration of sorbate, ultrasonic field technology
It closes, finally obtains small primary particle size, high degree of dispersion, few nanoscale dysprosium powder of reuniting, preparation method controls simple, cost
It is low, environmentally friendly, it is conducive to industrialized production.
Preparing nanoscale dysprosium powder with conventional citric acid method the macromolecules such as polyvinyl alcohol or polyethylene glycol must be added has
Machine additive is as dispersing agent difference, and the present invention selects sorbate and precipitating reagent with alkaline mixed solution is combined into, without adding
Increase molecule organic solvent, and be easily removed in the washing process of sorbate after the reaction, avoids causing in calcination process
The reunion of dysprosia.
Nanoscale dysprosium powder primary particle size produced by the present invention is small, high degree of dispersion, reunite it is few, conjecture be on the one hand by
Fast in reverse-precipitation nucleation rate, acid feed liquid containing dysprosium quickly forms spherical dysprosium carbonate particle after instillation, while upper
It states under mixing speed and ultrasonic field frequencies range, is accelerated into nuclear reaction progress, the generation of reaction solution ultrasound cavitation effect, effectively prevention
The reunion of intergranular, to inhibit further growing up for dysprosium carbonate particle secondary nucleation and nucleus；Simultaneously under certain acidity, hydrogen ion
Competitive relation is deposited to carbonate with dysprosium ion, causes nucleation rate much larger than the speed of growth, also inhibits dysprosium carbonate to a certain extent
Particle growth.
On the other hand, the sorb acid group in reaction solution can form soluble dysprosium complexing in conjunction with a small amount of metal dysprosium cation
Object, and such macromolecular chain dysprosium complex can play physical barrier, inhibit to reunite between particle, while dense in above-mentioned sorbate
Under degree, mixing speed and ultrasonic field frequencies range, it is easy to be formed hydroxyl and carboxyl on the sorb acid group of crystal brige originally with part of atoms,
Particle surface is not adsorbed in reaction solution, so that hard aggregation in dysprosium carbonate nucleation process is effectively avoided, and sorbate is dense
After spending height, alkaline mixed solution viscosity is increased, chemistry of the particle being nucleated in reaction solution in hydrogen ion and dysprosium complex hydroxyl
It is easily formed hard aggregation instead under key effect.
As acidity feed liquid containing dysprosium constantly instills, until the pH of the reaction solution is 5-7, sediment is no longer analysed in reaction solution
Out.Reaction solution is filtered out, obtained sediment is washed through volatile solvent, removes the residual moisture on sediment.
In the present invention, the sediment includes dysprosium carbonate and sorbic acid dysprosium complex etc..Due to sorbic acid dysprosium complex point
Solution temperature is lower with respect to dysprosium carbonate, and common one-step calcination is easy to make powder since temperature is quickly raised to dysprosium carbonate decomposition temperature
Body surfaces of tacky, usually surface atom is diffusion interlinked between particle, so that large-granule dysprosium oxide is generated, and the calcining of two steps can effectively delay
Solve the generation of such phenomenon.
To sum up, the present invention should be the dysprosium carbonate and the complexing of sorbic acid dysprosium that the process conditions such as low whipping speed and ultrasonic field obtain
Under object interaction, and by appropriate post-processing, small primary particle size, good dispersion, few nano oxidized dysprosium of reuniting are finally obtained
Powder.
In the embodiment of recommendation, the primary particle size of the nano oxidized dysprosium powder is 10nm-30nm.
The digital scope that the present invention announces includes all point values of this range.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment
The present invention will be further described in detail, but protection scope of the present invention is not limited to following embodiments.
In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition.
In the embodiment of recommendation, the precipitating reagent is in sodium carbonate, ammonium carbonate, sodium bicarbonate or ammonium hydrogen carbonate
It is at least one.
In the embodiment of recommendation, the alkaline mixed solution is added dropwise in ultrasonic field described acid containing dysprosium while stirring
Feed liquid forms reaction solution, controls 40 DEG C -60 DEG C of temperature of the reaction solution.Within the scope of this relative low temperature, crystal nucleation speed
Fastly, grain growth rate is slower, is more advantageous to and obtains tiny crystal grain；Temperature is improved, the viscosity of solution will be reduced, thus crystal
Nucleation rate reduces, and crystal grain growth rate is accelerated, and the crystal grain of acquisition is coarseer.
In the embodiment of recommendation, the speed of the stirring is 40r/min-60r/min, and the frequency of the ultrasonic field is
40kHz-60kHz.Mixing speed and ultrasonic field frequencies range are there are certain synergistic effect, and to obtain, partial size is small, of good dispersion
Grain, must promote forming core, and suppression growth prevents to reunite between particle, the hard aggregation left is especially difficult to resolve, in this mixing speed and ultrasonic field
Under frequency, reacts relatively mild, be difficult to form effective chemical binding force between particle, good dispersion small to final acquisition partial size
Dysprosia it is more beneficial.
In the embodiment of recommendation, the volatile solvent is selected from least one of acetone, ethyl alcohol or isopropanol.
Acetone, ethyl alcohol or isopropanol can effectively remove the residual moisture of deposit, reduce water polarity effect and caused by reunite influence,
On the other hand the sorbate for being adsorbed in sediment on a small quantity can remove together in company with washing process, further decrease powder and formed firmly
The risk of reunion, the preferred dehydrated alcohol of volatile solvent.
In the embodiment of recommendation, in every liter of alkaline mixed solution, the speed of the acid feed liquid containing dysprosium is added dropwise
For 60ml/min-80ml/min.
In the embodiment of recommendation, the drying temperature is 80 DEG C -120 DEG C, time 0.5h-2.5h.
In the embodiment of recommendation, the two steps calcining is included in 270 DEG C of -350 DEG C of progress first step calcinings, 850
DEG C -900 DEG C of progress second step calcinings.The composition of sediment includes dysprosium carbonate and sorbic acid dysprosium complex, and sorbate is at 270 DEG C
Start to be thermally decomposed, the two steps calcining by above-mentioned temperature effectively avoids powder surface tacky, occurs big partial size in dysprosia
Grain.
In the embodiment of recommendation, the reunion COEFFICIENT K a of the dysprosia powder is lower than 5.Reunion COEFFICIENT K a calculation formula
As follows, reflect the reunion degree of powder, closer to 1, reunion degree is smaller.
d50: dysprosia powder cumulative particle sizes percentile reaches partial size corresponding when 50%；
D: dysprosia primary particle size, the average grain diameter obtained using TEM (projection scanning electron microscope) observation.
In the embodiment of recommendation, the particle diameter distribution coefficients R of the dysprosia powder is lower than 0.5.Particle diameter distribution coefficients R
Calculation formula is as follows, reflects the particle size distribution range of powder, smaller, particle diameter distribution is narrower.
d90: dysprosia powder cumulative particle sizes percentile reaches partial size corresponding when 90%；
d10: dysprosia powder cumulative particle sizes percentile reaches partial size corresponding when 10%.
It should be noted that the selection of the concentration of dysprosium chloride and/or dysprosium nitrate, precipitating reagent and its concentration, dropwise addition acidity contain
The speed and drying temperature of dysprosium feed liquid and time are the conventional selections of the industry, are not tried in embodiment above range
It tests and verifies.
Embodiment one
1) prepare pH be 2, the acidity feed liquid containing dysprosium that the concentration of dysprosium chloride is 1.2mol/L；
2) alkaline mixed solution of containing sodium carbonate and sodium sorbate is prepared, the concentration of the sodium carbonate is 1.5mol/L, institute
The concentration for stating sodium sorbate is as shown in table 1；
3) the alkaline mixed solution side stirring, while the acid feed liquid containing dysprosium, every liter of alkali are added dropwise in ultrasonic field
Property mixed solution in, the speed that the acid feed liquid containing dysprosium is added dropwise is 80ml/min, reaction solution is formed, until the pH of the reaction solution
It is 7, obtains sediment；The frequency of the temperature of the reaction solution, the speed of stirring and ultrasonic field is as shown in table 1；
4) sediment is through acetone washing, 80 DEG C of drying 2.5h, then in 270 DEG C of progress first step calcinings, at 900 DEG C
Second step calcining is carried out, nano oxidized dysprosium powder is obtained.
Table 1
Embodiment two
1) prepare pH be 2.5, the acidity feed liquid containing dysprosium that the concentration of dysprosium nitrate is 2mol/L；
2) alkaline mixed solution containing ammonium carbonate and potassium sorbate is prepared, the concentration of the ammonium carbonate is 2.5mol/L, institute
The concentration for stating potassium sorbate is as shown in table 2；
3) the alkaline mixed solution side stirring, while the acid feed liquid containing dysprosium, every liter of alkali are added dropwise in ultrasonic field
Property mixed solution in, the speed that the acid feed liquid containing dysprosium is added dropwise is 60ml/min, reaction solution is formed, until the pH of the reaction solution
It is 5, obtains sediment；The frequency of the temperature of the reaction solution, the speed of stirring and ultrasonic field is as shown in table 2；
4) sediment is through dehydrated alcohol washing, 90 DEG C of drying 1h, then in 350 DEG C of progress first step calcinings, 850
DEG C carry out second step calcining, obtain nano oxidized dysprosium powder.
Table 2
Embodiment three
1) prepare pH be 3, the acidity feed liquid containing dysprosium that the concentration of dysprosium nitrate is 1.6mol/L；
2) alkaline mixed solution containing ammonium hydrogen carbonate and potassium sorbate is prepared, the concentration of the ammonium hydrogen carbonate is 2mol/L,
The concentration of the potassium sorbate is as shown in table 3；
3) the alkaline mixed solution side stirring, while the acid feed liquid containing dysprosium, every liter of alkali are added dropwise in ultrasonic field
Property mixed solution in, the speed that the acid feed liquid containing dysprosium is added dropwise is 70ml/min, reaction solution is formed, until the pH of the reaction solution
It is 6, obtains sediment；The frequency of the temperature of the reaction solution, the speed of stirring and ultrasonic field is as shown in table 3；
4) sediment is through isopropanol washing, 120 DEG C of drying 0.5h, then in 320 DEG C of progress first step calcinings,
880 DEG C of progress second step calcinings, obtain nano oxidized dysprosium powder.
Table 3
7 difference from Example 1 of comparative example is to replace sodium sorbate using sodium citrate.
8 difference from Example 1 of comparative example is after sediment drying using 900 DEG C of progress one-step calcinations.
The dysprosia obtained to each embodiment and comparative example performs the following performance tests:
1) primary particle size: statistical average partial size is observed using TEM, the results are shown in Table 4；
3) particle diameter distribution is tested: being detected to obtain the volume distribution of granularity using American-European gram particle size analyzer.
4) reunion COEFFICIENT K a and particle diameter distribution coefficients R, the results are shown in Table 4.
Table 4
As conclusion we it follows that
From table 4, it can be seen that the dysprosia prepared using the method for 1~comparative example of comparative example 6, primary particle size are significantly higher than
Each embodiment, while it is obvious to reflect that it is reunited much higher than each embodiment for reunite coefficient and particle diameter distribution coefficient.
Comparative example 7 may lack dispersing agent, while washing process solubility in volatile solvent is lower causes heavy
The residual of starch, when heating, cause serious agglomeration between particle.
8 one-step calcination of comparative example, quickly heating keeps particle surface tacky, occurs large-size particles in dysprosia.
The speed of stirring is 40r/min-60r/min, and the frequency of ultrasonic field is that partial size is small, divides to obtaining by 40kHz-60kHz
It is more beneficial to dissipate the good dysprosia powder of property, while mixing speed and ultrasonic field frequencies range have correlation with reacting liquid temperature.
The dysprosia data comparison of embodiment 5- embodiment 7 and comparative example 3- comparative example 4 can be seen that with sorbate
The increase of concentration, to being nucleated and nuclei growth being inhibited to play good effect, after further increasing, reaction fluid viscosity increases, between particle
Easy to reunite, dispersibility is deteriorated.
Above-described embodiment is only used for explaining technical solution provided by the present invention, can not limit the present invention
System, any simple modification, equivalent change and modification to the above embodiments, fall according to the technical essence of the invention
Enter in the protection scope of technical solution of the present invention.
Claims (8)
1. a kind of nano oxidized dysprosium raw powder's production technology, which comprises the following steps:
1) the acidity feed liquid containing dysprosium that pH is 2-3, the concentration of dysprosium chloride and/or dysprosium nitrate is 1.2mol/L-2mol/L is prepared；
2) alkaline mixed solution containing precipitating reagent and sorbate is prepared, the concentration of the precipitating reagent is 1.5mol/L-2.5mol/
L, the concentration of the sorbate are 0.012mol/L-0.2mol/L；
3) the acid feed liquid containing dysprosium is added dropwise in the alkaline mixed solution in ultrasonic field while stirring, forms reaction solution, control
The temperature of the reaction solution is lower than 65 DEG C, until the pH of the reaction solution is 5-7, obtains sediment；The speed of the stirring is
10r/min-100r/min, the frequency of the ultrasonic field are 40kHz-80kHz；
4) sediment is calcined through the washing of volatile solvent, drying and two steps, and the two steps calcining is included in 270 DEG C -350
DEG C carry out first step calcining in 850 DEG C of -900 DEG C of progress second step calcinings obtains nano oxidized dysprosium powder later.
2. a kind of nano oxidized dysprosium raw powder's production technology according to claim 1, it is characterised in that: the precipitating reagent choosing
From at least one of sodium carbonate, ammonium carbonate, sodium bicarbonate or ammonium hydrogen carbonate.
3. a kind of nano oxidized dysprosium raw powder's production technology according to claim 1, it is characterised in that: the alkalinity mixing
The acid feed liquid containing dysprosium is added dropwise in solution in ultrasonic field while stirring, forms reaction solution, controls the temperature 40 of the reaction solution
℃-60℃。
4. a kind of nano oxidized dysprosium raw powder's production technology according to claim 1, it is characterised in that: the volatile
Solvent is selected from least one of acetone, ethyl alcohol or isopropanol.
5. a kind of nano oxidized dysprosium raw powder's production technology according to claim 1, it is characterised in that: every liter of alkalinity
In mixed solution, the speed that the acid feed liquid containing dysprosium is added dropwise is 60ml/min-80ml/min.
6. a kind of nano oxidized dysprosium raw powder's production technology according to claim 1, it is characterised in that: the drying temperature
It is 80 DEG C -120 DEG C, time 0.5h-2.5h.
7. a kind of nano oxidized dysprosium raw powder's production technology according to claim 1, it is characterised in that: the dysprosia powder
The reunion COEFFICIENT K a of body is lower than 5, and the particle diameter distribution coefficients R of the dysprosia powder is lower than 0.5, and the Ka meetsInstitute
State d50Corresponding partial size when reaching 50% for dysprosia powder cumulative particle sizes percentile；The D is the primary grain of dysprosia
Diameter, the average grain diameter observed using TEM；The R meetsThe d90For the distribution of dysprosia powder cumulative particle sizes
Percentage reaches partial size corresponding when 90%；The d10Reach 10% when institute for dysprosia powder cumulative particle sizes percentile
Corresponding partial size.
8. a kind of nano oxidized dysprosium raw powder's production technology according to claim 3, it is characterised in that: the speed of the stirring
Degree is 40r/min-60r/min, and the frequency of the ultrasonic field is 40kHz-60kHz.
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| CN111017977A (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 dysprosium oxide for dielectric ceramic capacitor |
| CN111392757B (en) * | 2020-03-06 | 2022-09-23 | 江阴加华新材料资源有限公司 | Preparation method of nano dysprosium oxide |
| CN115246653B (en) * | 2022-07-12 | 2023-10-17 | 中南大学 | Nanometer dysprosium oxide and preparation method and application thereof |
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| CN103482670B (en) * | 2013-09-10 | 2014-09-24 | 中铝稀土（常熟）有限公司 | Method for preparing high-purity dysprosium oxide |
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