CN110240195A - A kind of preparation method of monoclinic zirconia nanometer product - Google Patents
A kind of preparation method of monoclinic zirconia nanometer product Download PDFInfo
- Publication number
- CN110240195A CN110240195A CN201910615495.1A CN201910615495A CN110240195A CN 110240195 A CN110240195 A CN 110240195A CN 201910615495 A CN201910615495 A CN 201910615495A CN 110240195 A CN110240195 A CN 110240195A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- monoclinic zirconia
- monoclinic
- preparation
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation methods of monoclinic zirconia nanometer product, it is characterized in that the following steps are included: using ammonium fluozirconate weak solution as initial feed, sealing after ammonium fluozirconate weak solution is placed in hydrothermal reaction kettle, adjusting temperature in hydrothermal reaction kettle is 200~500 DEG C, pressure is 80~120MPa, carry out itself 10~15h of hydrolysis, it is quickly cooled down after reaction, open reaction kettle, take out residual solution, then sample is collected, drying to obtain monoclinic zirconia product after washing, the monoclinic zirconia product is the monoclinic zirconia nano powder or monoclinic zirconia nano-coating product of uniform particle diameter.The preparation method uses ammonium fluozirconate ((NH4)2ZrF6) it is used as raw material, monoclinic phase zirconia nano-powder and its plated film are synthesized by single agents high-temperature hydrolysis, and monoclinic phase zirconia nanopowder powder particles are uniform, large specific surface area, purity is high.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation method of monoclinic zirconia nanometer product.
Background technique
Zirconium oxide (ZrO2) it is a kind of very important structure and function material, there are excellent physical and chemical properties,
Such as high-melting-point (up to 2700 DEG C), higher boiling, high rigidity, the thermal expansion coefficient that small thermal coefficient is small, big and good grain
Electron conductivity, and it is wear-resistant, high temperature resistant, corrosion-resistant and anti-oxidant.Since the 1980s, zirconium oxide is in addition to as tradition
Other than refractory material and ceramic glaze, the energy, environment and in terms of application also obtain more and more attention.And
Nano zircite because small size cause its optics, mechanics, thermodynamics and in terms of performance different from conventional material
Material, thus in commercial synthesis, catalyst and catalyst carrier, special cermacis, thermal barrier coating, refractory material, cutting tool, sensing
Device, solid state battery, decoration, absorption and activeness and quietness etc. have a very wide range of application value.
There are 3 kinds of paramorphs at different temperatures in zirconium oxide, i.e., room temperature to 1170 DEG C be monoclinic phase；1170~2370
DEG C be tetragonal phase；It is cubic phase higher than 2370 DEG C to fusing point.Due to the original of tetragonal phase and cubic phase zircite crystal inside configuration
Sub- electrostatic attraction is smaller, repulsive force is larger, and the stability of system is poor, therefore under cryogenic, tetragonal phase and cubic phase
It is easy to convert to monoclinic phase, monoclinic phase is more stable.The researchs such as Wang Jingjing also indicate that the physicochemical properties of zirconium oxide not only take
Certainly in its chemical component and phase structure, its pattern, size, surface area etc. are also depended on, this leads to every kind of unique microscopic appearance
Zirconium oxide all there is distinctive physics and chemical property.Therefore, in recent years, more and more method trials prepare different-shape
Nanometer zirconium oxide with size is to achieve the purpose that improving performance or developing new capability.So far, pass through physics or change
Learn synthetic method and successfully synthesized the zirconium oxide of different morphologies or structure, as nano powder, nanometer rods, nanofiber, nano wire,
Nano whisker, nanotube, microballoon, film and composite material etc..Wherein, zirconia nano-powder is because of its ultra-fine partial size, good
Dispersibility becomes a kind of novel high-performance inorganic structural material；Simultaneously as it is with biggish specific surface area, abundant
Surface duct and thermal stability, and there is weak acid, weak base and oxidation-reduction quality, it is a kind of excellent catalytic support material, it can also
Catalyst performance is improved as auxiliary agent.
Three classes, i.e. vapor phase method, liquid phase method and solid phase method can be summarized as by preparing zirconia nano-powder common method.Wherein liquid phase
Method prepares zirconia nano-powder because the advantages that its is at low cost, easy to operate, with high purity, yield is big and is easy to industrialization obtains extensively
Using during liquid phase method prepares zirconia nano-powder, traditional handicraft all uses zirconium raw material+precipitating reagent ± stabilizer ± molten
The plurality of raw materials reagent such as agent.It is mainly at present eight water oxygen zirconium chloride (ZrOCl using widest synthesis material2·8H2O), aqueous
Nitric acid oxidation zirconium (ZrO (NO3)2·xH2O), five water zirconium nitrates (Zr (NO3) 45H2O), zirconium chloride (ZrCl4), and with part
Inorganic or organic reagent is as precipitating reagent (such as sodium hydroxide, ammonium hydroxide, docusate sodium, urea), with part inorganic reagent work
For stabilizer (such as silver nitrate, calcium chloride, yttrium chloride, yttrium oxide), and using part organic reagent as solvent or polymerization inhibitor
(such as: polyethylene glycol, dehydrated alcohol, lauryl sodium sulfate, n-butanol, cyclohexane, isopropanol, positive ethyl alcohol, Span-80
Deng).Therefore, in the traditional handicraft of liquid phase method synthesis zirconia nano-powder, the zirconium source raw material type of use is more single, needs
In the new high-quality and cheap zirconium source raw material of further exploitation；Meanwhile a variety of inorganic and organic examination is used in traditional handicraft
Agent, portion of reagent is more rare and expensive, increases synthesis cost, so that synthesis technology is excessively complicated, also needs to simplify synthesis
Process reduces synthesis cost；Finally, the nano zircite that conventional synthesis goes out is mostly the mixing of monoclinic phase, tetragonal phase or cubic phase
Object, the nano zircite for synthesizing certain uniform, pure crystal form are the technologies for needing to improve in current process.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of monoclinic zirconia nanometer product, which uses fluorine
Zirconic acid ammonium ((NH4)2ZrF6) it is used as raw material, monoclinic phase zirconia nano-powder has been synthesized by single agents itself hydrolysis, and
Monoclinic phase zirconia nanopowder powder particles are uniform, and large specific surface area, purity is higher, meanwhile, this method can also be directly applied to metal
Surface forms one layer of highly porous monoclinic phase zirconia nanopowder plated film.
Above-mentioned purpose of the invention is achieved by the following technical solution: a kind of system of monoclinic zirconia nanometer product
Preparation Method, comprising the following steps: using ammonium fluozirconate weak solution as initial feed, ammonium fluozirconate weak solution is placed in hydrothermal reaction kettle
In after sealing, adjust hydrothermal reaction kettle in temperature be 200~500 DEG C, pressure be 80~120MPa, carry out itself hydrolysis 10
~15h, is quickly cooled down after reaction, opens reaction kettle, takes out residual solution, then collects sample, be drying to obtain after washing
To monoclinic zirconia product, the monoclinic zirconia product is that the monoclinic zirconia nano powder of uniform particle diameter or monoclinic zirconia are received
Rice plated film.
In the preparation method of the monoclinic zirconia nanometer product:
Preferably, temperature is 250~500 DEG C in the hydrothermal reaction kettle, and reaction pressure is 100~120MPa, is carried out certainly
Body 12~15h of hydrolysis, wherein itself hydrolysis time does not include heating and temperature fall time, is referred in set temperature and pressure
Itself hydrolysis time is carried out under power.Prepared product pattern and performance are more preferably.
Preferably, the concentration of the ammonium fluozirconate weak solution is 0.01~0.02mol/L.
As one of preferred embodiment of the invention, the ammonium fluozirconate weak solution is first placed in metal tube,
The metal tube equipped with ammonium fluozirconate weak solution is placed in hydrothermal reaction kettle again, the metal tube is inert metal pipe or alloy
Pipe；The inert metal Guan Weiyin, gold or platinum pipe, the compo pipe are gold-palladium or silver palladium alloy pipe；The ammonium fluozirconate
The volume of weak solution accounts for the 30%~80% of metal tube total volume.
As one of preferred embodiment of the invention, the hydrothermal reaction kettle include metal shell and be set to institute
The liner in metal shell is stated, the liner is plastics, inert metal or alloy strong alkali-acid resistance liner, wherein the plastics are
Polytetrafluoroethylene (PTFE), polybenzoate or polyimides, the inert metal are silver, gold or platinum, and the alloy is gold-palladium or silver-colored palladium,
The volume of the ammonium fluozirconate weak solution accounts for the 30%~80% of hydrothermal reaction kettle total volume.
As one of preferred embodiment of the invention, the hydrothermal reaction kettle include metal shell and be set to institute
The sheet metal of metal shell lower inside is stated, the metal is one or more of gold, silver and palladium, and the ammonium fluozirconate is dilute
The volume of solution accounts for the 30%~80% of hydrothermal reaction kettle total volume.
Preferably, it during preparing monoclinic phase zirconia nano-powder, adopts and inner wall of metal tube or hydro-thermal is washed with deionized
The liner of reaction kettle 2~3 times collects cleaning solution, cleaning solution is centrifuged, lower sediment is taken, and reuses deionized water and ethyl alcohol is first
It washs 2~3 times afterwards, obtains uniform monoclinic zirconia nano powder after dry, wherein dry use natural air drying or drying basin
It is dry.
Preferably, during preparing monoclinic phase zirconia metallic coated product, deionized water and ethanol washing are successively used
Metal product 2~3 times, the monoclinic zirconia nano powder plated film of the Different porosities of uniform particle diameter is obtained after dry, wherein doing
It is dry dry using natural air drying or drying basin.
Preferably, hydrothermal reaction kettle is heated using heating furnace to adjust hydro-thermal reaction temperature in the kettle, using inertia
Pressure in gas regulation hydrothermal reaction kettle, the inert gas are argon gas or helium.
Preferably, it is quickly cooled down and reaction kettle is rapidly cooled using ice water or compressed air.
Preferably, the residual solution is mainly ammonium fluozirconate, hydrofluoric acid and ammonium hydroxide；The ammonium fluozirconate can continue conduct
Initial feed uses.
The core of monoclinic zirconia process for preparing nm powder of the invention is to utilize ammonium fluozirconate single agents itself
The zirconium oxide nano crystal of hydrolysis generation monoclinic system.Using relatively inexpensive ammonium fluozirconate powder common in the market as zirconium
Source, is configured to certain density ammonium fluozirconate solution, and ammonium fluozirconate solution is put into hydrothermal reaction kettle, carries out to hydrothermal reaction kettle
It is heated and pressurizeed, after reaction, hydrothermal reaction kettle is rapidly cooled to room temperature, after deposit cleaning, drying obtained
It can be obtained uniform and higher degree monoclinic phase zirconia nano-powder or monoclinic phase zirconia nanopowder coated article.
In monoclinic zirconia process for preparing nm powder of the invention, unique core reagent used is ammonium fluozirconate, in water
Under heat condition, following hydrolysis occurs for ammonium fluozirconate and water:
(NH4)2ZrF6+2H2O→ZrO2↓+6HF+2NH3
The hydrolysis is the hydrolysis autoreaction of single agents, and synthesis zirconia nano-powder settles at one go, avoids tradition
The complicated technology of a variety of raw material such as zirconium source+precipitating reagent ± stabilizer ± solvent is used in technique.Due to passing through temperature and pressure
Nanocrystalline type and crystalline form are controlled, the carry out degree of above-mentioned hydrolysis is controlled by the reaction time, it is equal in order to obtain partial size
One, the good monoclinic phase zirconia nano-powder of crystal structure, needing to control above-mentioned hydrolysis is incomplete reaction, therefore residual
Remaining reaction solution mainly includes ammonium fluozirconate, hydrofluoric acid and ammonium hydroxide, and the ammonium fluozirconate solution of recycling can continue on for of the invention
Initial feed effectively can recycle and reduce cost.Simultaneously as the pyrohydrolysis of ammonium fluozirconate is substantially metal ion molten
Solubility supersaturation process in liquid can regulate and control the degree of super saturation and nanometer of metal ion by the height of control temperature
The growth closeness of crystal, therefore, this method may be directly applied to the zirconia nanopowder plated film of metal surface Different porosities, from
And it improves the corrosion-resistant, anti-of metal product and suppresses and physical characteristic resistant to high temperature.
Compared with prior art, the present invention has the advantage that
(1) the method for the present invention using ammonium fluozirconate as single agents, by ammonium fluozirconate under hydrothermal conditions itself
It is nanocrystalline that hydrolysis generates monoclinic zirconia, to realize that single agents autoreaction synthesizes monocline phase zircite zirconia nanopowder
Powder；
(2) the method for the present invention passes through the zirconia nano-powder of single agents autoreaction synthesized high-performance under liquid-phase condition,
Then nano powder is eluted using deionized water and ethyl alcohol, the advantages of this method inherits Traditional liquid phase method synthesis technology,
And whole synthesis technology only needs to avoid traditional work using ammonium fluozirconate and ethyl alcohol both common, cheap reagent raw materials
Using the proportion weighing of the patterns controlling agents such as a variety of expensive predecessors, precipitating reagent, stabilizer and solvent and successively during skill
Processing step, thus this method simple process, it is easily operated control, cost is relatively low；
(3) the method for the present invention mainly carries out under the conditions of 200~500 DEG C, synthesizes stable and high-purity monoclinic phase oxygen
Change zirconium nano powder, reaction temperature is low, avoids the condition of 600 DEG C~1200 DEG C high temperature, avoids complicated reaction, calcining, clearly
It the processes such as washes, simplifies technique, substantially increase the safety of synthesis technology, while also reducing synthesis cost；
(4) the monoclinic zirconia nano powder that the method for the present invention is synthesized by the incomplete hydrolysis of ammonium fluozirconate itself,
Purity is high, and nanometer powder particles are uniform, large specific surface area has a good application prospect；
(5) present invention directly can form the monoclinic phase oxygen of Different porosities in metal surface by complex compound pyrohydrolytic method
Change zirconium nano-coating, enriches nano material coating technique.
Detailed description of the invention
Fig. 1 be 200 magnification micrographs (a) of monoclinic phase zirconia nano-powder prepared in the embodiment of the present invention 1 and
Stereoscan photograph (b)~(d) of different enlargement ratios, wherein (b) being 10,000 times of amplification；It (c) is 20,000 times of amplification；It (d) is to put
It is 30,000 times big；
Fig. 2 is 50 magnification micrographs (a) and 1 of the monoclinic phase zirconia nano-powder prepared in the embodiment of the present invention 2
Ten thousand times of stereoscan photographs (b)；
Fig. 3 is the scanning electricity of the monoclinic phase zirconia nano-powder difference enlargement ratio prepared in the embodiment of the present invention 3
Mirror photo, (a) are 20,000 times of amplification；It (b) is 40,000 times of amplification；
Fig. 4 be 200 magnification micrographs (a) of monoclinic phase zirconia nano-powder prepared in the embodiment of the present invention 4 and
Stereoscan photograph (b)~(d) of different enlargement ratios, wherein (b) being 10,000 times of amplification；It (c) is 30,000 times of amplification；It (d) is to put
It is 20,000 times big；
Fig. 5 be 200 magnification micrographs (a) of monoclinic phase zirconia nano-powder prepared in the embodiment of the present invention 5 and
Stereoscan photograph (b)~(d) of different enlargement ratios, wherein (b) being 10,000 times of amplification；It (c) is 10,000 times of amplification；It (d) is to put
It is 20,000 5 thousand times big；
Fig. 6 is the scanning electricity of the monoclinic phase zirconia nano-powder difference enlargement ratio prepared in the embodiment of the present invention 6
Mirror photo, (a) are 10,000 8 thousand times of amplification；It (b) is 50,000 times of amplification；
Fig. 7 be 200 magnification micrographs (a) of monoclinic phase zirconia nano-powder prepared in the embodiment of the present invention 7 and
The stereoscan photograph of different enlargement ratios, wherein (b) being 10,000 5 thousand times of amplification；It (c) is 20,000 5 thousand times of amplification；It (d) is amplification 5
Wan Bei；
Fig. 8 is the monoclinic phase zirconia nano-powder and standard monocline phase zircite prepared in 1-7 of the embodiment of the present invention
The laser Raman spectroscopy comparison diagram of crystal.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is further illustrated, but the scope of protection of present invention is for example anti-
Device and the volume of reaction temperature, reaction time and reaction liquid is answered to be not limited to the embodiment and lifted.
Embodiment 1
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) by 0.48g ammonium fluozirconate ((NH4)2ZrF6, purity 99%, West Asia reagent, similarly hereinafter) it is dissolved in 100L deionized water
In sufficiently dissolve be made 0.02mol/L reaction solution, by reaction solution obtained put into 200mL hydrothermal reaction kettle, hydro-thermal reaction
Kettle is sealed high-temp high-pressure reaction kettle, and high-temperature high-pressure reaction kettle is connected with high-precision ultra high pressure table, ventilation pipe and cut-off
Valve, high-temperature high-pressure reaction kettle have metal shell, and polytetrafluoroethyllining lining is equipped in metal shell, after reaction kettle is tightened,
Argon gas is injected into kettle by ventilation pipe to pressure 50MPa, shut-off valve is closed and stops gas injection, by heating furnace to reaction kettle into
Row heating, setting reaction temperature are 200 DEG C；
(2) temperature rises to after 200 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure 80MPa,
It is kept for the reaction time 12 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling to room temperature；
(3) reaction kettle in step (1) is opened, recycles residual solution in kettle, using deionized water washing kettle Nell wall, received
Nano zirconium dioxide turbid can be obtained in the fluid of collection washing, and gained turbid is placed in centrifuge and is centrifuged, after centrifugation
It takes out lower sediment and is rinsed 2~3 times with deionized water and dehydrated alcohol, finally grain will can be obtained after sediment natural air drying
The uniform more pure monoclinic phase zirconia nano-powder of diameter.
Step (3) uses the Nell wall of deionized water washing kettle, collects and does not need ethyl alcohol in the flow liquid process of washing, by gained
Turbid is placed in centrifuge and is centrifuged, and lower sediment is taken out after centrifugation and rinses 2~3 with deionized water and dehydrated alcohol
It is secondary, after centrifugation after type-approval process need dehydrated alcohol because water will lead to nano powder and reunite, and dehydrated alcohol energy
The generation reunited is avoided, so sizing must first use deionized water when dry, finally uses ethyl alcohol, the two sequence cannot overturn.
(a) figure shows that zirconia nanopowder powder particles are smaller in Fig. 1, seemingly plates membranaceous.
(b)~(d) figure illustrates the pattern and particle size of zirconia nano-powder under different enlargement ratios in Fig. 2, can be with
See, nano powder is in rice-shaped, and partial size is several nanometer~200 nanometer, is concentrated mainly on 150~200 nanometers.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 200 DEG C is obvious, clearly
14 Raman scattering peaks similar with standard monocline phase zircite crystal are indicated to Chu, show the zirconia nano-powder master of synthesis
If monoclinic phase.In addition to this, in 258cm-1、612cm-1And 640cm-1Place also shows 3 faint Raman scattering peaks, with
3 in the typical Raman scattering of 6 of tetragonal phase zirconium oxide peak can be mapped, this shows to synthesize under the conditions of 200 DEG C
Zirconia nano-powder be although but to be also mixed with the tetragonal phase zirconium oxide of few ratio based on monoclinic phase.Due to LR laser raman peak
There are certain corresponding relationships between ingredient by force, and the peak intensity of the monoclinic zirconia LR laser raman by comparing 100% purity pushes away
It surveys the tetragonal phase zirconium oxide ratio mixed in synthetic and is no more than 5%.
Embodiment 2
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) 0.24g ammonium fluozirconate is dissolved in 100mL deionized water sufficiently to dissolve and 0.01mol/L reaction solution is made, it will
The reaction solution 5mL of preparation carries out sealing after putting into diameter 4.5mm gold tube, then puts gold tube into high-temperature high-voltage reaction
Kettle after tightening reaction kettle, argon gas is injected by ventilation pipe to pressure 80MPa into kettle, closes shut-off valve and stop gas injection, pass through
Heating furnace heats reaction kettle, and setting reaction temperature is 250 DEG C；
(2) temperature rises to after 250 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure
100MPa is kept for the reaction time 12 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling extremely
Room temperature；
(3) reaction kettle in step (1) is opened, the gold tube taking-up in step (2) is broken, makes to be washed with deionized
Golden inside pipe wall, the fluid for collecting washing can be obtained nano zircite turbid, gained turbid are placed in centrifuge and is centrifuged, from
Lower sediment is taken out after the heart and is successively rinsed 2~3 times with deionized water and ethyl alcohol, finally will be after sediment natural air drying
Monoclinic phase zirconia nano-powder can be obtained.
(a) figure microphoto shows the monoclinic phase zirconia nano-powder sprayed on gold inside pipe wall in Fig. 2；(b) figure in Fig. 2
Stereoscan photograph shows that monoclinic phase zirconia nanopowder powder particles are uniform, and partial size is tens nanometers~200 nanometers.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 250 DEG C is obvious, clearly
Indicate to Chu with the one-to-one 14 Raman scattering peaks of standard monocline phase zircite crystal, and do not show that other apparent are dissipated
Peak is penetrated, shows that the zirconia nano-powder of synthesis is entirely monoclinic phase.
Embodiment 3
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) 0.48g ammonium fluozirconate is dissolved in 100mL deionized water sufficiently to dissolve and 0.02mol/L reaction solution is made, it will
Reaction solution obtained puts into hydrothermal reaction kettle, places a flat gold slice in reactor bottom, after reaction kettle is tightened,
Argon gas is injected into kettle by ventilation pipe to pressure 80MPa, shut-off valve is closed and stops gas injection, by heating furnace to reaction kettle into
Row heating, setting reaction temperature are 250 DEG C；
(2) temperature rises to after 250 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure
120MPa is kept for the reaction time 10 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling extremely
Room temperature；
(3) reaction kettle in step (1) is opened, recycles residual solution in kettle, the gold taken out in step (1) in kettle is thin
Piece is successively washed 2~3 times using deionized water and ethyl alcohol, and there are one layer of nano oxygens on visible gold slice surface after natural air drying
Change zirconium plated film.
(a) figure and (b) figure show that the metal coating scanning electron microscope of the zirconia nano-powder under different enlargement ratios is shone in Fig. 3
Piece, display nano-crystalline granule is uniform, and based on rice-shaped and ellipticity, partial size is tens nanometers~200 rans.Zirconium oxide
It is the hole of 400~1000 nanosizeds between nanometer powder crystal.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 250 DEG C is obvious, clearly
Indicate to Chu with the one-to-one 14 Raman scattering peaks of standard monocline phase zircite crystal, and do not show that other apparent are dissipated
Peak is penetrated, shows that the zirconia nano-powder of synthesis is entirely monoclinic phase, is the monoclinic phase zirconia nanopowder coated article of high-purity.
Embodiment 4
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) 0.24g ammonium fluozirconate is dissolved in 100mL deionized water sufficiently to dissolve and 0.01mol/L reaction solution is made, it will
Reaction solution obtained puts into hydrothermal reaction kettle, places a flat gold slice in reactor bottom, after reaction kettle is tightened,
Argon gas is injected into kettle by ventilation pipe to pressure 50MPa, shut-off valve is closed and stops gas injection, by heating furnace to reaction kettle into
Row heating, setting reaction temperature are 300 DEG C；
(2) temperature rises to after 300 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure 80MPa,
It is kept for the reaction time 10 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling to room temperature；
(3) reaction kettle in step (1) is opened, recycles residual solution in kettle, the gold taken out in step (1) in kettle is thin
Piece is successively washed 2~3 times using deionized water and dehydrated alcohol, and there are one layer on visible gold slice surface after natural air drying to receive
Rice zirconium oxide plated film.
(a) figure is the microphoto on gold material surface in Fig. 4, shows the zirconia nano-powder plated film of fine particle shape；
(b), (c) and (d) figure are the zirconia nano-powder stereoscan photograph of different enlargement ratios in Fig. 4, and display nano-crystalline granule is equal
One, based on rice-shaped and ellipticity, partial size is tens nanometers~250 rans.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 300 DEG C is obvious, clearly
Indicate to Chu with the one-to-one 14 Raman scattering peaks of standard monocline phase zircite crystal, show synthesis zirconia nanopowder
Powder main body is monoclinic phase.In addition to this, in 258cm-1And 640cm-1Place also shows 2 very faint Raman scattering peaks, with
2 in the typical Raman scattering of 6 of tetragonal phase zirconium oxide peak can be mapped, this shows to synthesize under the conditions of the present embodiment
Although zirconia nano-powder main body out is based on monoclinic phase, single tetragonal phase zirconium oxide for being also mixed with considerably less ratio.This may
Lower pressure (80MPa) is used with the present embodiment and the less reaction time (10 hours) is related, if pressure improved
To 100MPa, the reaction time is improved to 12 hours or more, and remaining tetragonal phase zirconium oxide should be able to be completely converted into monoclinic phase oxygen
Change zirconium, to obtain the higher monoclinic phase zirconia nano-powder of purity.
Embodiment 5
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) 0.48g ammonium fluozirconate is dissolved in 100mL deionized water sufficiently to dissolve and 0.02mol/L reaction solution is made, it will
The reaction solution 5mL of preparation carries out sealing after putting into diameter 4.5mm gold tube, then puts gold tube into high-temperature high-voltage reaction
Kettle after tightening reaction kettle, argon gas is injected by ventilation pipe to pressure 80MPa into kettle, closes shut-off valve and stop gas injection, pass through
Heating furnace heats reaction kettle, and setting reaction temperature is 400 DEG C；
(2) temperature rises to after 400 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure
100MPa is kept for the reaction time 15 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling extremely
Room temperature；
(3) reaction kettle in step (1) is opened, recycles residual solution in kettle, the gold taken out in step (1) in kettle is thin
Piece is successively washed 2~3 times using deionized water and ethyl alcohol, and there are one layer of nano oxygens on visible gold slice surface after natural air drying
Change zirconium plated film.
(a) figure is the microphoto on gold material surface in Fig. 5, shows the zirconia nano-powder plated film of fine particle shape；
(b), (c) and (d) figure show the zirconia nano-powder stereoscan photograph under different enlargement ratios in Fig. 5, show nanocrystalline
Grain is more uniform, and based on rice-shaped, partial size is 100 nanometers~200 rans.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 400 DEG C is obvious, clearly
Indicate to Chu with the one-to-one 14 Raman scattering peaks of standard monocline phase zircite crystal, and do not show that other apparent are dissipated
Peak is penetrated, shows that the zirconia nano-powder of synthesis is entirely monoclinic phase.
Embodiment 6
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) 0.24g ammonium fluozirconate is dissolved in 100mL deionized water sufficiently to dissolve and 0.01mol/L reaction solution is made, it will
The reaction solution 5mL of preparation carries out sealing after putting into diameter 4.5mm gold tube, then puts gold tube into high-temperature high-voltage reaction
Kettle after tightening reaction kettle, argon gas is injected by ventilation pipe to pressure 100MPa into kettle, closes shut-off valve and stop gas injection, lead to
It crosses heating furnace to heat reaction kettle, setting reaction temperature is 400 DEG C；
(2) temperature rises to after 400 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure
120MPa is kept for the reaction time 10 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling extremely
Room temperature；
(3) reaction kettle in step (1) is opened, recycles residual solution in kettle, the gold taken out in step (1) in kettle is thin
Piece is successively washed 2~3 times using deionized water and ethyl alcohol, can get monoclinic phase zirconia nano-powder after natural air drying.
(a) figure and (b) figure are the stereoscan photograph of the zirconia nano-powder film plating layer under different enlargement ratios in Fig. 6,
Show that nano-crystalline granule is uniform, based on rice-shaped, corynebacterium and bulk, partial size is 100 nanometers~300 rans.Oxidation
Porosity is lower between zirconium nano particle, and about tens nanometers.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 400 DEG C is obvious, clearly
Indicate to Chu with the one-to-one 14 Raman scattering peaks of standard monocline phase zircite crystal, and do not show that other apparent are dissipated
Peak is penetrated, shows that the zirconia nano-powder of synthesis is entirely monoclinic phase.
Embodiment 7
The preparation method of monoclinic zirconia nano powder provided in this embodiment, comprising the following steps:
(1) 0.24g ammonium fluozirconate is dissolved in 100mL deionized water sufficiently to dissolve and 0.01mol/L reaction solution is made, it will
Reaction solution obtained puts into hydrothermal reaction kettle, places a flat gold slice in reactor bottom, after reaction kettle is tightened,
Argon gas is injected into kettle by ventilation pipe to pressure 80MPa, shut-off valve is closed and stops gas injection, by heating furnace to reaction kettle into
Row heating, setting reaction temperature are 500 DEG C；
(2) temperature rises to after 500 DEG C, shut-off valve in opening steps (1), continues supplement injection argon gas to pressure
100MPa is kept for the reaction time 12 hours, pours reaction kettle in leaching step (1) using ice water after the reaction was completed and carry out fast cooling extremely
Room temperature；
(3) reaction kettle in step (1) is opened, recycles residual solution in kettle, the gold taken out in step (1) in kettle is thin
Piece is successively washed 2~3 times using deionized water and ethyl alcohol, and there are one layer of nano oxygens on visible gold slice surface after natural air drying
Change zirconium plated film.
(a) figure is the microphoto on gold material surface in Fig. 7, shows the zirconia nano-powder plated film of fine particle shape；
(b), (c) and (d) figure are the zirconia nano-powder stereoscan photograph of different enlargement ratios in Fig. 7, and display nano-crystalline granule is equal
One, based on rice-shaped, corynebacterium and bulk, partial size is tens nanometers~300 rans.
Fig. 8 laser Raman spectroscopy shows that the zirconia nano-powder Raman scattering peak synthesized under the conditions of 500 DEG C is obvious, clearly
Indicate to Chu with the one-to-one 14 Raman scattering peaks of standard monocline phase zircite crystal, and do not show that other apparent are dissipated
Peak is penetrated, shows that the zirconia nano-powder of synthesis is entirely monoclinic phase.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of monoclinic zirconia nanometer product, it is characterized in that the following steps are included: with ammonium fluozirconate weak solution
For initial feed, sealing after ammonium fluozirconate weak solution is placed in hydrothermal reaction kettle, adjust temperature in hydrothermal reaction kettle be 200~
500 DEG C, pressure is 80~120MPa, carries out itself 10~15h of hydrolysis, is quickly cooled down after reaction, opens reaction kettle,
Taking-up residual solution, then collects sample, drying to obtain monoclinic zirconia product after washing, and the monoclinic zirconia product is
The monoclinic zirconia nano powder or monoclinic zirconia nano-coating of uniform particle diameter.
2. the preparation method of monoclinic zirconia nanometer product according to claim 1, it is characterized in that: in the hydrothermal reaction kettle
Temperature is 250~500 DEG C, and reaction pressure is 100~120MPa, carries out itself 12~15h of hydrolysis, and wherein itself hydrolysis is anti-
Do not include heating and temperature fall time between seasonable, refers to and carry out itself hydrolysis time under set temperature and pressure.
3. the preparation method of monoclinic zirconia nanometer product according to claim 1 or claim 2, it is characterized in that: the ammonium fluozirconate
The concentration of weak solution is 0.01~0.02mol/L.
4. the preparation method of monoclinic zirconia nanometer product according to claim 3, it is characterized in that: the ammonium fluozirconate is dilute molten
Liquid is first placed in metal tube, then the metal tube equipped with ammonium fluozirconate weak solution is placed in hydrothermal reaction kettle, and the metal tube is
Inert metal pipe or compo pipe；The inert metal Guan Weiyin, gold or platinum pipe, the compo pipe are gold-palladium or silver palladium alloy
Pipe；The volume of the ammonium fluozirconate weak solution accounts for the 30%~80% of metal tube total volume.
5. the preparation method of monoclinic zirconia nanometer product according to claim 3, it is characterized in that: the hydrothermal reaction kettle packet
Metal shell and the liner set on the metal shell inner surface are included, the liner is plastics, inert metal or the resistance to strong acid of alloy
Highly basic liner, wherein the plastics are polytetrafluoroethylene (PTFE), polybenzoate or polyimides, the inert metal is silver, gold or platinum
Gold, the alloy are gold-palladium or silver-colored palladium, the volume of the ammonium fluozirconate weak solution account for hydrothermal reaction kettle total volume 30%~
80%.
6. the preparation method of monoclinic zirconia nanometer product according to claim 3, it is characterized in that: the hydrothermal reaction kettle packet
Include metal shell and the sheet metal set on the metal shell lower inside, the metal be one of gold, silver and palladium or
Several, the volume of the ammonium fluozirconate weak solution accounts for the 30%~80% of hydrothermal reaction kettle total volume.
7. the preparation method of monoclinic zirconia nanometer product according to claim 4 or 5, it is characterized in that: using deionized water
Liner 2~3 times for washing inner wall of metal tube or hydrothermal reaction kettle collect cleaning solution, cleaning solution are centrifuged, lower sediment is taken, then
It is successively washed 2~3 times using deionized water and ethyl alcohol, uniform monoclinic zirconia nano powder is obtained after dry, wherein drying
It is dry using natural air drying or drying basin.
8. the preparation method of monoclinic zirconia nanometer product according to claim 6 is adopted it is characterized in that: collecting sheet metal
It is successively washed sheet metal 2~3 times with deionized water and dehydrated alcohol, the Different porosities of uniform particle diameter is obtained after dry
Monoclinic zirconia nano powder plated film, wherein dry dry using natural air drying or drying basin.
9. the preparation method of monoclinic zirconia nanometer product according to claim 3, it is characterized in that: using heating furnace to hydro-thermal
Reaction kettle is heated to adjust hydro-thermal reaction temperature in the kettle, adjusts pressure in hydrothermal reaction kettle using inert gas, described lazy
Property gas be argon gas or helium；It is quickly cooled down and reaction kettle is rapidly cooled using ice water or compressed air.
10. the preparation method of monoclinic zirconia nanometer product according to claim 3, it is characterized in that: the residual solution master
It to be ammonium fluozirconate, hydrofluoric acid and ammonium hydroxide；The ammonium fluozirconate can continue to use as initial feed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910615495.1A CN110240195B (en) | 2019-07-09 | 2019-07-09 | Preparation method of monoclinic zirconia nano product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910615495.1A CN110240195B (en) | 2019-07-09 | 2019-07-09 | Preparation method of monoclinic zirconia nano product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110240195A true CN110240195A (en) | 2019-09-17 |
| CN110240195B CN110240195B (en) | 2020-10-23 |
Family
ID=67891478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910615495.1A Active CN110240195B (en) | 2019-07-09 | 2019-07-09 | Preparation method of monoclinic zirconia nano product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110240195B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111573728A (en) * | 2020-05-15 | 2020-08-25 | 浙江金琨锆业有限公司 | Pure monoclinic phase nano-grade zirconium dioxide powder with ultrahigh specific surface area and preparation method thereof |
| CN111673632A (en) * | 2020-06-22 | 2020-09-18 | 河源帝诺新材料有限公司 | Preparation method of nano-grade zirconium oxide grinding medium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241865A (en) * | 2016-08-23 | 2016-12-21 | 中国科学院广州地球化学研究所 | The preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline |
| CN106335922A (en) * | 2016-08-23 | 2017-01-18 | 中国科学院广州地球化学研究所 | Preparation method of high(001)-crystal-facet ultrathin anatase nanosheet self-assembled microspheres |
| CN108163892A (en) * | 2018-03-16 | 2018-06-15 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction prepares octahedra crystal form Ta2O5The method of nano particle |
| CN108264087A (en) * | 2018-03-16 | 2018-07-10 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction, which prepares to have, aligns Nb2O5The method of nanometer rods |
-
2019
- 2019-07-09 CN CN201910615495.1A patent/CN110240195B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241865A (en) * | 2016-08-23 | 2016-12-21 | 中国科学院广州地球化学研究所 | The preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline |
| CN106335922A (en) * | 2016-08-23 | 2017-01-18 | 中国科学院广州地球化学研究所 | Preparation method of high(001)-crystal-facet ultrathin anatase nanosheet self-assembled microspheres |
| CN108163892A (en) * | 2018-03-16 | 2018-06-15 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction prepares octahedra crystal form Ta2O5The method of nano particle |
| CN108264087A (en) * | 2018-03-16 | 2018-07-10 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction, which prepares to have, aligns Nb2O5The method of nanometer rods |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111573728A (en) * | 2020-05-15 | 2020-08-25 | 浙江金琨锆业有限公司 | Pure monoclinic phase nano-grade zirconium dioxide powder with ultrahigh specific surface area and preparation method thereof |
| CN111573728B (en) * | 2020-05-15 | 2022-04-19 | 浙江金琨锆业有限公司 | Pure monoclinic phase nano-grade zirconium dioxide powder with ultrahigh specific surface area and preparation method thereof |
| CN111673632A (en) * | 2020-06-22 | 2020-09-18 | 河源帝诺新材料有限公司 | Preparation method of nano-grade zirconium oxide grinding medium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110240195B (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106241865B (en) | It is a kind of high（001）The nanocrystalline preparation method of face anatase titanium dioxide | |
| Patil et al. | Synthesis techniques and applications of rare earth metal oxides semiconductors: A review | |
| CN107052356A (en) | A kind of preparation method of the tungsten yittrium oxide superfine composite precursor powder of core shell structure | |
| CN105060351B (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| CN110240195A (en) | A kind of preparation method of monoclinic zirconia nanometer product | |
| CN106335922B (en) | A kind of preparation method of the ultra-thin anatase nanometer sheet self-assembly microspheres in height (001) face | |
| CN102464323A (en) | Method for preparing high-purity superfine zirconium boride powder by high-frequency plasma | |
| CN106044849A (en) | Technology for preparing nano-metallic oxide powder with DC (direct-current) plasma method | |
| CN106048730B (en) | A kind of method of titanium alloy differential arc oxidation preparing nano titanium dioxide ceramic whisker | |
| CN106365194A (en) | Preparation method of lanthanum titanate nanometer material | |
| CN104961159B (en) | A kind of nanometer tungsten oxide and one step vapour phase reduction preparation method and application | |
| CN106216664B (en) | A kind of method preparing monocrystalline spherical shape silver nano-grain and the silver nano-grain being consequently formed | |
| CN102070178A (en) | Method for preparing yttrium oxide micro-nano-materials based on hydrothermal technology regulation and control | |
| CN105731518B (en) | Normal-temperature crystallization preparation method of octahedron cuprous oxide crystal | |
| CN110921705A (en) | Preparation method of yttrium tantalate powder based on solvothermal method | |
| Mosavari et al. | Nano-ZrO2: A review on synthesis methodologies | |
| Yang et al. | Liquid–solid–solution synthesis of ultrafine Gd2Zr2O7 nanoparticles with yield enhancement | |
| CN104817107B (en) | A kind of method of preparing black titanium dioxide B phase and anatase-phase nano particle | |
| CN109422293B (en) | Preparation method of micron-sized spherical cobaltosic oxide material | |
| CN108500285A (en) | It is a kind of to support or the preparation method of non-supported transition metal@h-BN core-shell structure copolymer nanostructures | |
| CN110217818A (en) | Uniform particle size zirconium dioxide nanosphere and its film and preparation method | |
| CN108946812A (en) | Alkali tungsten bronze nanometer rods and its preparation method and application | |
| CN100496745C (en) | Method for preparing line shape or stick shape polycrystalline Ce06Zr03Y01O2 solid solution | |
| CN109534410A (en) | A kind of preparation method of single layered porous cobaltosic oxide nano piece | |
| CN111333128B (en) | Preparation method of high-uniformity nickel oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |