CN105271404A - Method for preparing nano hafnium oxide with different crystal forms through controlling seeds - Google Patents
Method for preparing nano hafnium oxide with different crystal forms through controlling seeds Download PDFInfo
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- CN105271404A CN105271404A CN201510724076.3A CN201510724076A CN105271404A CN 105271404 A CN105271404 A CN 105271404A CN 201510724076 A CN201510724076 A CN 201510724076A CN 105271404 A CN105271404 A CN 105271404A
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- hafnium
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Abstract
The invention relates to a method for preparing nano hafnium oxide with different crystal forms through controlling seeds. The method comprises the following steps: under a room-temperature condition, dropwisely adding an hafnium oxychloride solution into a sodium oleate water solution, and adding cyclohexane and stirring to obtain a mixed solution; taking tetragonal crystal form or monoclinic-crystal-form hafnium oxide nano particles as the seeds and adding the seeds into the cyclohexane, and carrying out ultrasonic dispersion to obtain seed suspending liquid; transferring the mixed solution into a high-pressure reaction kettle; dropwisely adding the seed suspending liquid and a sodium hydroxide solution in sequence; keeping an oil-water volume ratio of the system to (1:1) and keeping the temperature at 120 DEG C for 24 hours; separating an oil phase, washing and centrifuging, and drying to obtain the product. The method provided by the invention has the characteristics of simple operation method, good repeatability, easy-to-control reaction conditions, lower requirements on temperatures, no need of roasting and the like; the crystal forms of the product are controlled by controlling the crystal forms of the added seeds; prepared high-quality oil-soluble nano hafnium oxide particles have uniformly-distributed grain diameters and good dispersity, and have a good application prospect.
Description
Technical field
The invention belongs to the preparation field of hafnium oxide material, particularly a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium.
Background technology
Hafnium oxide is a kind of stupalith with broad-band gap and high-k, is particularly caused concern extremely in the application of microelectronic.In addition, it can also as refractory materials, radioresistance coating and catalyzer.
At present, about nanometer HfO
2preparation method have a lot, mainly contain hydrothermal method, sol-gel method, microemulsion method, coprecipitation method etc.Though these methods can obtain nanometer HfO
2particle, but all there is certain shortcoming.Particle size distribution prepared by hydrothermal method is wider; The raw material of sol-gel method usually costly, is not easy to suitability for industrialized production; Microemulsion method need through follow-up high-temperature roasting, and the powder dispersity obtained is poor, high degree of agglomeration.
Water-oil interface method is the method for a kind of new synthesis of nano particle proposed in recent years, has simple to operate, and reaction conditions is gentle, and size tunable, product purity is high, and productive rate is high, good crystallinity, good dispersity, and particle diameter is little, and cost is low, the advantage that efficiency is high.In patent CN102267728A, the favorable dispersity that Zhou Xingping etc. adopt this method to synthesize, to have particle size extremely tiny, the oil soluble Fe that purity is high
3o
4nano particle, can be dispersed in oil phase for a long time, is easy to preserve.2013, Zhou Xingping etc. adopted this method successfully to synthesize the oil soluble TiO of good dispersity, size tunable
2nano particle [ColloidsandSurfacesA:Physicochem.Eng.Aspects423 (2013) 115-123].And the nano particle that the seed law is prepared, easy to control in size, better dispersed, and adding of seed can make correspondingly to be obtained by reacting lifting.Therefore, the hafnium oxide nano particle of the preparation that these two kinds of methods combined has size tunable, the advantages such as dispersiveness is better, and reaction conditions is gentle, without aftertreatments such as roastings.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium, and the inventive method is simple to operate, reproducible, and reaction conditions is easily controlled, and temperature requirement is lower, without the need to roasting; The even particle size distribution of the nanometer titanium dioxide hafnium particle obtained, good dispersity, has a good application prospect.
A kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium of the present invention, comprising:
(1) under room temperature condition, oxychlorination hafnium solution is added drop-wise in aqueous solution sodium oleate, then adds hexanaphthene, stir, obtain mixing solutions; Wherein the mol ratio of oxychlorination hafnium, sodium oleate is 1:2;
(2) by the hafnium oxide HfO of tetragonal structure or monoclinic form
2nano particle, as seed, adds in hexanaphthene, ultrasonic disperse, obtains seed suspension liquid;
(3) mixing solutions of step (1) is transferred in autoclave, and successively drips seed suspension liquid, sodium hydroxide solution, and keep the profit volume ratio of system to be 1:1, then at 120 DEG C of constant temperature 24h, be separated oil phase, wash centrifugal, drying, obtains nanometer titanium dioxide hafnium.
In described step (1), the concentration of oxychlorination hafnium solution is 0.2M; The concentration of aqueous solution sodium oleate is 0.2M.
In described step (1), the volume ratio of oxychlorination hafnium solution, hexanaphthene is 1:4.
In described step (1), churning time is 2-3h.
Tetragonal structure or monoclinic form hafnium oxide HfO in the middle seed of step (3)
2hf in nano particle and mixing solutions
4+mol ratio 0.1:1.
In described step (3), the concentration of sodium hydroxide solution is 3M.
In described step (3), washing is centrifugal is: ethanol, deionized water alternately wash centrifugal.
Described ethanol, deionized water alternately wash and are centrifugally: first use absolute ethanol washing, centrifugation 10min centrifugal segregation supernatant liquor under 10000rpm, use deionized water wash again, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, circulation like this 3 times, finally uses absolute ethanol washing, centrifugation 15min is centrifugal under 10000rpm.
In described step (3), drying temperature is 50 ~ 60 DEG C.
beneficial effect
(1) to have working method simple, reproducible in the present invention, and reaction conditions is easily controlled, and temperature requirement is lower, without the need to features such as roastings;
(2) the present invention can control the crystal formation of product by the crystal formation controlling to add seed;
(3) the present invention prepares the even particle size distribution of excellent oil solubility nanometer hafnium oxide particle, and good dispersity, has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the method;
Fig. 2 is the XRD figure of oil soluble hafnium oxide nano particle of reference examples 1 (brilliant without planting), embodiment 1 (four directions is planted brilliant), embodiment 2 (monocline kind is brilliant) gained;
Fig. 3 is the TEM figure of the oil soluble hafnium oxide nano particle of reference examples 1 gained;
Fig. 4 is the TEM figure of the oil soluble tetragonal structure hafnium oxide nano particle of embodiment 1 gained;
Fig. 5 is the TEM figure of the oil soluble monoclinic form hafnium oxide nano particle of embodiment 2 gained.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Reference examples 1
(1) take 0.609g sodium oleate, 40 DEG C are dissolved in the deionized water of 10ml.After sodium oleate dissolves completely, add 0.2mol/L oxychlorination hafnium solution 5ml, be precipitated.In system, add the hexanaphthene of 20ml again, room temperature lower magnetic force stirs 2 ~ 3h, to aqueous phase water white transparency, oil phase oyster white, is transferred to 100ml high-pressure hydrothermal reaction kettle.
(2) in reactor, drip the hexanaphthene of 5ml.
(3) sodium hydroxide taking 3g is dissolved in the deionized water of 10ml, is added drop-wise to (profit volume ratio is 1:1) in reactor.
(4) reactor is placed in air dry oven, under 120 DEG C of conditions, reacts 24h.
(5) after reaction terminates, naturally cool to after room temperature until high-pressure hydrothermal reaction kettle, first use absolute ethanol washing, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, use deionized water wash again, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, circulation like this 3 times, finally with absolute ethanol washing, under 10000rpm, centrifugation 15min is centrifugal is precipitated, finally 60 DEG C of dryings in air dry oven, namely obtain hafnium oxide particle.
As can be seen from the TEM of XRD and Fig. 3 of Fig. 2, product is the mixture of the nanometer titanium dioxide hafnium particle of tetragonal structure and monoclinic form.
Embodiment 1
(1) take 0.609g sodium oleate, 40 DEG C are dissolved in the deionized water of 10ml.After sodium oleate dissolves completely, add 0.2mol/L oxychlorination hafnium solution 5ml, be precipitated.In system, add the hexanaphthene of 20ml again, room temperature lower magnetic force stirs 2 ~ 3h, to aqueous phase water white transparency, oil phase oyster white, is transferred to 100ml high-pressure hydrothermal reaction kettle.
(2) HfO of the tetragonal structure of 0.0105g is taken
2nano particle, is dispersed in the hexanaphthene of 5ml, and ultrasonic 30min obtains seed suspension liquid.This suspension liquid is added drop-wise in reactor, makes the Zr in seed and mixed solution
4+mol ratio be 0.1.
(3) sodium hydroxide taking 3g is dissolved in the deionized water of 10ml, is added drop-wise to (in system profit volume ratio 1:1) in reactor.
(4) reactor is placed in air dry oven, under 120 DEG C of conditions, reacts 24h.
(5) after reaction terminates, naturally cool to after room temperature until high-pressure hydrothermal reaction kettle, first use absolute ethanol washing, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, use deionized water wash again, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, circulation like this 3 times, finally with absolute ethanol washing, under 10000rpm, centrifugation 15min is centrifugal is precipitated, finally 50 DEG C of dryings in air dry oven, namely obtain zirconium dioxide particle.
Schemed by the TEM of XRD and Fig. 4 of Fig. 2, can find out, product is all the nanometer titanium dioxide hafnium particle of tetragonal structure, and grain diameter is about 5.0nm.
Embodiment 2
(1) take 0.609 sodium oleate, 40 DEG C are dissolved in the deionized water of 10ml.After sodium oleate dissolves completely, add 0.2mol/L zirconyl chloride solution 5ml, be precipitated.In system, add the hexanaphthene of 20ml again, room temperature lower magnetic force stirs 2 ~ 3h, to aqueous phase water white transparency, oil phase oyster white, is transferred to 100ml high-pressure hydrothermal reaction kettle.
(2) ZrO of the monoclinic form of 0.0105g is taken
2nano particle, is dispersed in the hexanaphthene of 5ml, and ultrasonic 30min obtains seed suspension liquid.This suspension liquid is added drop-wise in reactor, makes the Zr in seed and mixed solution
4+mol ratio be 0.1.
(3) sodium hydroxide taking 3g is dissolved in the deionized water of 10ml, is added drop-wise to (in system profit volume ratio 1:1) in reactor.
(4) reactor is placed in air dry oven, under 120 DEG C of conditions, reacts 24h.
(5) after reaction terminates, naturally cool to after room temperature until high-pressure hydrothermal reaction kettle, first use absolute ethanol washing, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, use deionized water wash again, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, circulation like this 3 times, finally with absolute ethanol washing, under 10000rpm, centrifugation 15min is centrifugal is precipitated, finally 60 DEG C of dryings in air dry oven, namely obtain zirconium dioxide particle.
Schemed by the TEM of XRD and Fig. 5 of Fig. 2, can find out, product is all the nano zirconium dioxide particle of monoclinic form, and grain diameter is about 80.0nm.
Claims (9)
1., by controlling a method for Spawn preparation different crystal forms nanometer titanium dioxide hafnium, comprising:
(1) under room temperature condition, oxychlorination hafnium solution is added drop-wise in aqueous solution sodium oleate, then adds hexanaphthene, stir, obtain mixing solutions; Wherein the mol ratio of oxychlorination hafnium, sodium oleate is 1:2;
(2) by the hafnium oxide HfO of tetragonal structure or monoclinic form
2nano particle, as seed, adds in hexanaphthene, ultrasonic disperse, obtains seed suspension liquid;
(3) mixing solutions of step (1) is transferred in autoclave, and successively drips seed suspension liquid, sodium hydroxide solution, and keep the profit volume ratio of system to be 1:1, then at 120 DEG C of constant temperature 24h, be separated oil phase, wash centrifugal, drying, obtains nanometer titanium dioxide hafnium.
2. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: in described step (1), the concentration of oxychlorination hafnium solution is 0.2M; The concentration of aqueous solution sodium oleate is 0.2M.
3. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: in described step (1), the volume ratio of oxychlorination hafnium solution, hexanaphthene is 1:4.
4. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: in described step (1), churning time is 2-3h.
5. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: tetragonal structure or monoclinic form hafnium oxide HfO in the middle seed of step (3)
2hf in nano particle and mixing solutions
4+mol ratio 0.1:1.
6. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: in described step (3), the concentration of sodium hydroxide solution is 3M.
7. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: in described step (3), washing is centrifugal is: ethanol, deionized water alternately wash centrifugal.
8. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 7, it is characterized in that: described ethanol, deionized water alternately wash and be centrifugally: first use absolute ethanol washing, centrifugation 10min centrifugal segregation supernatant liquor under 10000rpm, use deionized water wash again, centrifugation 15min centrifugal segregation supernatant liquor under 10000rpm, circulation like this 3 times, finally uses absolute ethanol washing, centrifugation 15min is centrifugal under 10000rpm.
9. a kind of method by controlling Spawn preparation different crystal forms nanometer titanium dioxide hafnium according to claim 1, is characterized in that: in described step (3), drying temperature is 50 ~ 60 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108330540A (en) * | 2018-04-12 | 2018-07-27 | 山东大学 | Hafnium oxide single crystal fiber and the preparation method and application thereof |
| CN114906874A (en) * | 2022-06-17 | 2022-08-16 | 中国科学院高能物理研究所 | Hafnium oxide nano-particles and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN103693689A (en) * | 2013-12-19 | 2014-04-02 | 东华大学 | Method of synthesizing nano t-ZrO2 particles between oil-water interfaces by utilizing seed crystal method |
| CN103708548A (en) * | 2013-12-31 | 2014-04-09 | 东华大学 | Method for synthetizing monoclinic crystal zirconium dioxide nanoparticles between oil water interfaces by using seed crystal method |
-
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- 2015-10-29 CN CN201510724076.3A patent/CN105271404A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN103693689A (en) * | 2013-12-19 | 2014-04-02 | 东华大学 | Method of synthesizing nano t-ZrO2 particles between oil-water interfaces by utilizing seed crystal method |
| CN103708548A (en) * | 2013-12-31 | 2014-04-09 | 东华大学 | Method for synthetizing monoclinic crystal zirconium dioxide nanoparticles between oil water interfaces by using seed crystal method |
Non-Patent Citations (1)
| Title |
|---|
| AMENEH SAHRANESHIN ET AL.: "Surfactant-Assisted Hydrothermal Synthesis of Water-Dispersible Hafnium Oxide Nanoparticles in Highly Alkaline Media", 《CRYSTAL GROWTH & DESIGN》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108330540A (en) * | 2018-04-12 | 2018-07-27 | 山东大学 | Hafnium oxide single crystal fiber and the preparation method and application thereof |
| CN108330540B (en) * | 2018-04-12 | 2020-09-04 | 山东大学 | Hafnium oxide single crystal optical fiber and preparation method and application thereof |
| CN114906874A (en) * | 2022-06-17 | 2022-08-16 | 中国科学院高能物理研究所 | Hafnium oxide nano-particles and preparation method and application thereof |
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Application publication date: 20160127 |