CN108640677A - A kind of nano composite oxides zirconium powder preparation that crystallite dimension is controllable - Google Patents
A kind of nano composite oxides zirconium powder preparation that crystallite dimension is controllable Download PDFInfo
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Abstract
The present invention provides a kind of hydrothermal preparing process of crystallite dimension controllable nano compound zirconium oxide powder.Using zirconates and yttrium salt as initial soln, precipitating reagent is added into solution, ageing filtering, filter cake is distributed in water, and it is transferred in autoclave and carries out hydro-thermal reaction, composite mineralizer is added in reaction process by way of high-pressure injection, is centrifuged after reaction, is dried to obtain the controllable nano composite oxides zirconium powder body of high-crystallinity crystallite dimension.The present invention, which solves the small distribution width of crystallite dimension in existing hydro-thermal synthesis process, can not regulate and control and the problem of crystal grain is easily reunited.Nano zirconium oxide powder high dispersive prepared by the present invention, high-crystallinity, crystal form are tetragonal phase, and crystallite dimension is adjustable in 5 100 nanometer ranges, and grain size distribution is narrow.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of nano composite oxides zirconium powder that crystallite dimension is controllable
Preparation.
Background technology
Zirconium oxide is a kind of good, anticorrosive with high-melting-point (about 2700 DEG C), higher boiling, high intensity, high temperature resistant, wearability
The metal oxide materials of function admirable.In zirconium oxide it is compound enter small amounts yttrium Zirconium powder can be allowed to protect at room temperature
Tetragonal phase crystal structure is held, reduces ceramic post sintering in the process due to fault of construction caused by phase transformation.Nano level compound zirconia
Powder has been developed many important uses because also having nano-meter characteristic, is widely used in structural ceramics (such as bearing, valve
Door, cutter and grinding-material etc.), function ceramics (such as lambda sensor, solid oxide fuel cell, mobile phone dorsal shield and artificial tooth
Deng), the fields such as super toughening ceramic and zirconium cerium eutectic.Crystallite dimension is uniform, tetragonal phase crystal form ratio height, high-crystallinity, group
It is the key that prepare high quality zircite product to gather few nano composite oxides zirconium powder body.
Common nano composite oxides zirconium synthesis method includes：Coprecipitation, hydrolysis methods, sol-gel method,
Hydro-thermal method, microemulsion method and spray pyrolysis.Wherein hydro-thermal method is in special closed reaction vessel (autoclave), with solvent
As reaction medium, the reaction environment of high temperature and pressure is createed by heating reaction vessel, makes usual indissoluble or insoluble object
The method that matter is re-dissolved and recrystallized, the process conditions of reaction kettle are generally 120-250 DEG C of temperature in existing hydro-thermal method, press
Power 0.4-2.0MPa needs to use higher pressure when temperature is relatively low.From nineteen eighty-two, hydro-thermal method be used to prepare superfine for the first time
Since powder, hydro-thermal method relies on it without high-temperature calcination, product granularity is thin, reunites many advantages, such as few, obtains both domestic and external extensive
Concern, be prepare well-crystallized, few one of the preferred method of superfine ceramic powder of reuniting.However, synthesizing nanometer with hydro-thermal method
The prior art of zirconium oxide, the product grains size range such as CN200510045013, CN200610053923, synthesis are smaller only
5-15 nanometers, and it is uncontrollable.CN01130825 realizes the nanoscale zirconia of size tunable using the method for reverse micro emulsion
Synthesis, but the controlled range of its final products crystallite dimension is small, is also only 4.1-18.8 nanometers.
The powder product that existing nano zircite hydrothermal synthesis method is obtained, grain size range are uncontrollable or controllable
Range very little cannot meet downstream product to the diversified demand of crystallite dimension, it is therefore desirable to develop crystallite dimension controlled range
Wide nano zircite hydrothermal synthesis method.
Invention content
It is an object of the invention to solve the defect of prior art and provide a kind of crystallite dimension, controllable and controlled range is big
The nano zirconium oxide powder hydrothermal preparing process of (wide scope narrow ditribution).
To achieve the above object, the technical solution adopted by the present invention is：
A kind of nano composite oxides zirconium raw powder's production technology that crystallite dimension is controllable, comprises the following steps：
(1) soluble zirconates, yttrium salt are added to the water stirring and dissolving, precipitant solution is added, adjusted pH value, quickly stir
It mixes, obtain white emulsion and is aged；
(2) after being aged, filtration washing obtains filter cake, and filter cake is re-dispersed into water (preferably deionized water), high
Speed dispersion mashing obtains zirconium precursor somaplasm material；
(3) it shifts in zirconium precursor somaplasm material to autoclave and carries out hydro-thermal process, during which with high-pressure injection mode to kettle
Interior addition composite mineralizer, cools down after reaction, and separation obtains nano composite oxides zirconium powder body after dry.
In step (1) of the present invention, pH value is adjusted to 8-10, mixing speed 300-1000rpm.
In step (1) of the present invention, aging condition is 25-90 DEG C, digestion time 2-6h.
In step (2) of the present invention, mashing rotating speed is 300-1000rpm, a concentration of 0.2- of zirconium hydroxide in slurry
1.5mol/L。
In step (3) of the present invention, volume loading of the slurry in kettle is 70-80%, hydro-thermal process temperature 100-170
DEG C, preferably 120-150 DEG C, pressure 0.2-0.7MPa, reaction time 12-24h, mixing speed 300-1000rpm.
In the present invention, mineralizer is added during hydro-thermal process in 0.5-4h, is preferably added in 1-2h, the injection of mineralizer
Pressure is higher than reacting kettle inner pressure 0.05MPa.Step (3) controls zirconium oxide by controlling the concentration of mineralizer and the time being added
Crystallite dimension and its distribution.
In the present invention, the zirconates is zirconium oxychloride and/or zirconium nitrate, and the yttrium salt is yttrium chloride and/or yttrium nitrate；
In preferred steps (1), zirconates concentration 0.1-1.5mol/L in aqueous solution, yttrium salt concentration 0.004-0.24mol/L.
In the present invention, the precipitating reagent is two or more in ammonium hydroxide, urea, ammonium hydrogen carbonate and ammonium carbonate；It is preferred that heavy
Shallow lake agent solution concentration 5-15mol/L.
In the present invention, the composite mineralizer includes mineralizer A and mineralizer B, the mineralizer A are triisopropanolamine
And/or diisopropanolamine (DIPA), mineralizer B are one or both of malonamide, succinamide, butyramide；Preferably, in system
Mineralizer A concentration 0.1-0.5mol/L, more preferable 0.2-0.4mol/L, mineralizer B concentration 0.1-1mol/L, more preferable 0.3-
0.8mol/L。
In the present invention, the nano combined oxygen of the wide scope narrow ditribution of 5-100 nanometers of grain size can be obtained using the above method
Change zirconium powder body.
When hydro-thermal method prepares nano composite oxides zirconium, nano zircite is since the small surface energy of crystal grain is high, in oersted Wa Er
In moral maturing process, part little crystal grain can be gradually dissolved into solution system, and regrow neighboring die surface, promote crystalline substance
Grain is grown up.The present invention realizes that the controllable mechanism of Zirconium powder crystallite dimension is：
(1) regulate and control mineralising agent concentration：Its ordered aggregation is of different sizes in the reaction system for the mineralizer of various concentration, mine
The addition of agent plays the role of crystal growth soft template, to realize the controllable growth of crystallite dimension.
(2) mineralizer feed postition：At the initial stage of hydro-thermal reaction, zirconium precursor body crystallization is grown to small zirconia grains
When, mineralizer is added with the mode of high-pressure injection, crystallite dimension is controlled by controlling injection length and injection rate (concentration)；And
Mineralizer and presoma are added into reaction kettle together in the prior art, and zirconium precursor body crystallization process is influenced by mineralizer, are prepared
Grain size differ and dispersion effect is poor.
(3) mineralizer type is selected：Compared with traditional mineralizer (sodium chloride, ammonium chloride, triethanolamine etc.), alcohol amine amide
Class composite mineralizer has stronger dispersibility, the nano composite oxides zirconium powder body of preparation is without bright since its steric hindrance acts on
Aobvious agglomeration.
Compared with prior art, the positive effect of the present invention is：
1. the present invention can realize product grains size from 5- by adjusting the concentration and injection length of composite mineralizer
It is arbitrary controllable in 100 nanometer ranges, and grain size distribution is narrow；
2. nano zirconium oxide powder prepared by the present invention is pure tetragonal structure, no monoclinic form, product is uniformly dispersed, rolls into a ball
It is poly- few；
3. the reaction temperature in the present invention is relatively low, only 100-170 DEG C, reactor pressure is less than 0.7MPa, avoids existing
The severe production conditions of method high temperature high pressure, to the of less demanding of equipment；
4. the preparation method of the present invention is at low cost, stable quality, is easy to large-scale production.
Description of the drawings
Fig. 1：The XRD spectrum of nano composite oxides zirconium powder body in embodiment 1；
Fig. 2：The SEM photograph of nano composite oxides zirconium powder body in embodiment 1；
Fig. 3：The SEM photograph of nano composite oxides zirconium powder body in embodiment 2；
Fig. 4：The SEM photograph of nano composite oxides zirconium powder body in embodiment 3；
Fig. 5：The SEM photograph of nano composite oxides zirconium powder body in comparative example 1.
Specific implementation method
With reference to specific embodiment, the following further describes the technical solution of the present invention, and embodiment gives specifically
Embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment and comparative example raw material is as follows：
Embodiment and comparative example stock chart
| Title | Purity | Manufacturer |
| Basic zirconium chloride | ZrO2>=36.0% | Dongfang Zirconium Industry Science-Technology Co., Ltd., Guangdong |
| Zirconium nitrate | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Yttrium chloride | 99.999% | Jining Zhong Kai new materials Co., Ltd |
| Yttrium nitrate | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Ammonium hydroxide | 25-28wt% | Xi Long science limited liability company |
| Urea | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Ammonium hydrogen carbonate | It analyzes pure | Xi Long science limited liability company |
| Ammonium carbonate | It analyzes pure | Xi Long science limited liability company |
| Sodium hydroxide | It analyzes pure | Xi Long science limited liability company |
| Triisopropanolamine | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Diisopropanolamine (DIPA) | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Malonamide | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Succinamide | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Butyramide | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
The crystal form of nano composite oxides zirconium powder body and crystallite dimension by X ray diffracting spectrum (XRD, D8 Advance,
Brooker AXS companies) it calculates；The crystal morphology of nano composite oxides zirconium powder body by scanning electron microscope (SEM, SU8010,
Hitachi, Japan) it is observed.
Embodiment 1
By 32.06g basic zirconium chlorides, 1.41g yttrium chlorides are added in 900ml water, stir 15 minutes to basic zirconium chloride and chlorine
Change yttrium to be completely dissolved, mixing speed 400rpm.The ammonium hydroxide of 5mol/L, urea, ammonium hydrogen carbonate mixed solution are slowly added drop-wise to
It in the aqueous solution of basic zirconium chloride/yttrium chloride, quickly stirs, mixing speed 400rpm, adjusts pH=8.0,30 DEG C of Aging Temperature is old
Change 3 hours.
Reaction emulsion after ageing is poured into Buchner funnel and is filtered, deionized water is washed to filtrate and 0.1mol/L nitre
Sour silver solution reaction does not become cloudy.Filter cake is taken out, water is added to stir, mixing speed 400rpm is dispersed into the zirconium precursor body of 700ml
Slurry (a concentration of 0.26mol/L of zirconium hydroxide in slurry).
Zirconium precursor somaplasm material is transferred in the polytetrafluoro liner autoclave that volume is 1000ml, loading 70%,
Triisopropanolamine and succinamide is added to system to reaction system in (pressure about 0.25MPa in kettle) after 110 DEG C of reactions 3.5 hours
Both middle concentration respectively reaches 0.15mol/L and 0.2mol/L, injection pressure 0.3MPa, sustained response 12.5 hours.Reaction
It persistently stirs in the process, rotating speed 400rpm.Reaction terminates, and waits for that temperature of reaction kettle is cooled to room temperature, and product is realized through centrifuge
It is separated by solid-liquid separation.Solid product is freeze-dried, obtains nano composite oxides zirconium powder body.
Fig. 1 is the XRD spectrum of the nano composite oxides zirconium powder body, from collection of illustrative plates as can be seen that uppermost test diffraction maximum
It fits like a glove with nethermost standard tetragonal phase zirconium oxide peak (JCPDS no.50-1089), no monoclinic phase miscellaneous peak, product form
For tetragonal phase.Fig. 2 is the electron scanning micrograph of the nano composite oxides zirconium powder body, as can be seen from the figure nano oxidized
Zirconium powder body average grain size is about 20 nanometers, and grain size distribution is narrow, high dispersive, high-crystallinity.
Embodiment 2
By 128.25g basic zirconium chlorides, 22.52g yttrium chlorides are added in 900ml water, stirring 15 minutes to basic zirconium chloride and
Yttrium chloride is completely dissolved, mixing speed 600rpm.The ammonium hydroxide of 10mol/L, ammonium hydrogen carbonate mixed solution are slowly added drop-wise to chlorine
It in the aqueous solution of zirconium oxide/yttrium chloride, quickly stirs, mixing speed 600rpm, adjusts pH=9.0,60 DEG C of Aging Temperature, ageing
4 hours.
Reaction emulsion after ageing is poured into Buchner funnel and is filtered, deionized water is washed to filtrate and 0.1mol/L nitre
Sour silver solution reaction does not become cloudy.Filter cake is taken out, water is added to stir, mixing speed 600rpm is dispersed into the zirconium precursor body of 750ml
Slurry (a concentration of 0.96mol/L of zirconium hydroxide in slurry).
Zirconium precursor somaplasm material is transferred in the polytetrafluoro liner autoclave that volume is 1000ml, loading 75%,
Triisopropanolamine and succinamide is added to system to reaction system in (pressure about 0.35MPa in kettle) after 135 DEG C of reactions 2.5 hours
Both middle concentration respectively reaches 0.3mol/L and 0.5mol/L, injection pressure 0.4MPa, sustained response 18 hours.Reaction process
In persistently stir, rotating speed 600rpm.Reaction terminates, and waits for that temperature of reaction kettle is cooled to room temperature, and product is realized solid-liquid through centrifuge
Separation.Solid product is freeze-dried, obtains nano composite oxides zirconium powder body.
Fig. 3 is the electron scanning micrograph of the nano composite oxides zirconium powder body, as can be seen from the figure nano oxidized
Zirconium powder body average grain size is about 50 nanometers, and grain size distribution is narrow, high dispersive, high-crystallinity.
Embodiment 3
By 463.67g zirconium nitrates, 66.19g yttrium nitrates are added in 900ml water, stir 15 minutes to zirconium nitrate and nitric acid
Yttrium is completely dissolved, mixing speed 800rpm.The ammonium hydroxide of 12mol/L, urea, ammonium carbonate mixed solution are slowly added drop-wise to nitric acid
It in the aqueous solution of zirconium/yttrium nitrate, quickly stirs, mixing speed 800rpm, adjusts pH=10.0, it is small to be aged 5 for 90 DEG C of Aging Temperature
When.
Reaction emulsion after ageing is poured into Buchner funnel and is filtered, deionized water is washed to filtrate and 0.1mol/L nitre
Sour silver solution reaction does not become cloudy.Filter cake is taken out, water is added to stir, mixing speed 800rpm is dispersed into the zirconium precursor body of 800ml
Slurry (a concentration of 1.35mol/L of zirconium hydroxide in slurry).
Zirconium precursor somaplasm material is transferred in the polytetrafluoro liner autoclave that volume is 1000ml, loading 80%,
Diisopropanolamine (DIPA) and malonamide and butyryl is added to reaction system in (pressure about 0.6MPa in kettle) after 160 DEG C of reactions 1 hour
Concentration respectively reaches 0.45mol/L and 0.9mol/L both in amine mixed solution to system, and injection pressure 0.65MPa continues
Reaction 22.5 hours.It is persistently stirred in reaction process, rotating speed 800rpm.Reaction terminates, and waits for that reaction kettle is cooled to room temperature, by product
It realizes and is separated by solid-liquid separation through centrifuge.Solid product is freeze-dried, obtains nano composite oxides zirconium powder body.
Fig. 4 is the electron scanning micrograph of the nano composite oxides zirconium powder body, as can be seen from the figure nano oxidized
Zirconium powder body average grain size is about 85 nanometers, and grain size distribution is narrow, high dispersive, high-crystallinity.Comparative example 1
By 32.06g basic zirconium chlorides, 1.41g yttrium chlorides are added in 900ml water, stir 15 minutes to basic zirconium chloride and chlorine
Change yttrium to be completely dissolved, mixing speed 400rpm.The ammonium hydroxide of 5mol/L, urea, ammonium hydrogen carbonate mixed solution are slowly added drop-wise to
It in the aqueous solution of basic zirconium chloride/yttrium chloride, quickly stirs, mixing speed 400rpm, adjusts pH=8.0,60 DEG C of Aging Temperature is old
Change 3 hours.
Reaction emulsion after ageing is poured into Buchner funnel and is filtered, deionized water is washed to filtrate and 0.1mol/L nitre
Sour silver solution reaction does not become cloudy.Filter cake is taken out, water is added to stir, mixing speed 400rpm is dispersed into the zirconium precursor body of 700ml
Slurry (a concentration of 0.26mol/L of zirconium hydroxide in slurry).
Zirconium precursor somaplasm material is transferred in the polytetrafluoro liner autoclave that volume is 1000ml, loading 70%,
Mineralizer ammonium chloride is added simultaneously so that a concentration of 0.3mol/L of mineralizer in system, mechanical agitation are uniformly mixed, turn for 5 minutes
Fast 400rpm.Reaction kettle is closed, sustained response 12.5 hours, pressure about 1.43MPa in kettle under the conditions of 200 DEG C.In reaction process
Lasting stirring, rotating speed 400rpm.Reaction terminates, and waits for that reaction kettle is cooled to room temperature, and product is realized through centrifuge and is separated by solid-liquid separation.Gu
Body product is freeze-dried, obtains nano composite oxides zirconium powder body.
Fig. 5 is the electron scanning micrograph of the nano composite oxides zirconium powder body, as can be seen from the figure nano oxidized
Zirconium powder body average grain size is about 5 nanometers, and grain size distribution is very wide, and intergranular reunion is than more serious.
Claims (10)
1. a kind of nano composite oxides zirconium raw powder's production technology that crystallite dimension is controllable, comprises the following steps：
(1) soluble zirconates, yttrium salt are added to the water stirring and dissolving, precipitant solution is added, adjusted pH value, quickly stir, obtain
To white emulsion and it is aged；
(2) after being aged, filtration washing obtains filter cake, and filter cake is re-dispersed into water, and high speed dispersion is beaten before obtaining zirconium
Drive somaplasm material；
(3) it shifts in zirconium precursor somaplasm material to autoclave and carries out hydro-thermal process, during which added into kettle with high-pressure injection mode
Enter composite mineralizer, cool down after reaction, detach, nano composite oxides zirconium powder body is obtained after dry.
2. the preparation method of Zirconium powder according to claim 1, which is characterized in that pH value is adjusted in step (1)
8-10, mixing speed 300-1000rpm.
3. the preparation method of Zirconium powder according to claim 1, which is characterized in that aging condition is in step (1)
25-90 DEG C, digestion time 2-6h.
4. the preparation method of Zirconium powder according to claim 1, which is characterized in that in step (2), mashing rotating speed is
300-1000rpm, a concentration of 0.2-1.5mol/L of zirconium hydroxide in slurry.
5. the preparation method of Zirconium powder according to claim 1, which is characterized in that in step (3), slurry is in kettle
Volume loading be 70-80%, 100-170 DEG C of hydro-thermal process temperature, preferably 120-150 DEG C, pressure 0.2-0.7MPa, reaction
Time 12-24h, mixing speed 300-1000rpm.
6. the preparation method of Zirconium powder according to claim 1 or 5, which is characterized in that during hydro-thermal process
Mineralizer is added when 0.5-4h, is preferably added in 1-2h, the injection pressure of mineralizer is higher than reacting kettle inner pressure 0.05MPa.
7. zirconium oxide preparation method according to any one of claim 1-3, which is characterized in that the zirconates is oxychlorination
Zirconium and/or zirconium nitrate, the yttrium salt are yttrium chloride and/or yttrium nitrate；In preferred steps (1), zirconates concentration in aqueous solution
0.1-1.5mol/L, yttrium salt concentration 0.004-0.24mol/L.
8. zirconium oxide preparation method according to any one of claim 1-3, which is characterized in that the precipitating reagent is ammonia
Two or more in water, urea, ammonium hydrogen carbonate and ammonium carbonate；It is preferred that precipitant solution concentration 5-15mol/L.
9. the zirconium oxide preparation method according to any one of claim 1-8, which is characterized in that the composite mineralizer
Including mineralizer A and mineralizer B, the mineralizer A are triisopropanolamine and/or diisopropanolamine (DIPA), mineralizer B is malonyl
One or both of amine, succinamide, butyramide；Preferably, mineralizer A concentration 0.1-0.5mol/L in system, more preferably
0.2-0.4mol/L, mineralizer B concentration 0.1-1mol/L, more preferable 0.3-0.8mol/L.
10. according to claim 1-9 any one of them zirconium oxide preparation methods, which is characterized in that can be obtained using this method
Obtain the nano composite oxides zirconium powder body of the wide scope narrow ditribution of 5-100 nanometers of grain size.
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| CN111320479A (en) * | 2020-03-06 | 2020-06-23 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide material, preparation method and application thereof |
| CN112266244A (en) * | 2020-10-14 | 2021-01-26 | 安徽元琛环保科技股份有限公司 | Preparation method of high-sintering-activity zirconium oxide powder |
| CN113461051A (en) * | 2021-08-17 | 2021-10-01 | 焦作市维纳科技有限公司 | Preparation method of nano zirconia powder |
| CN114014651A (en) * | 2021-09-10 | 2022-02-08 | 王必庆 | Method for producing nano composite zirconia powder by hydrothermal method |
| CN115490263A (en) * | 2022-09-23 | 2022-12-20 | 上海大学 | Preparation method of nano zirconia powder |
| CN115584501A (en) * | 2022-10-26 | 2023-01-10 | 中国航发沈阳黎明航空发动机有限责任公司 | Corrosive for showing macroscopic crystal defects of nickel-based superalloy single crystal blade and application thereof |
| CN115611641A (en) * | 2022-10-19 | 2023-01-17 | 中国科学院赣江创新研究院 | Magnesium oxide and yttrium oxide powder and preparation method and application thereof |
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| CN112266244A (en) * | 2020-10-14 | 2021-01-26 | 安徽元琛环保科技股份有限公司 | Preparation method of high-sintering-activity zirconium oxide powder |
| CN113461051A (en) * | 2021-08-17 | 2021-10-01 | 焦作市维纳科技有限公司 | Preparation method of nano zirconia powder |
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| CN115611641B (en) * | 2022-10-19 | 2023-10-13 | 中国科学院赣江创新研究院 | Magnesia yttrium oxide powder and preparation method and application thereof |
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