CN109721357A - A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable - Google Patents
A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable Download PDFInfo
- Publication number
- CN109721357A CN109721357A CN201910196936.9A CN201910196936A CN109721357A CN 109721357 A CN109721357 A CN 109721357A CN 201910196936 A CN201910196936 A CN 201910196936A CN 109721357 A CN109721357 A CN 109721357A
- Authority
- CN
- China
- Prior art keywords
- zirconium oxide
- preparation
- yttrium
- hzo
- solution
- 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.)
- Pending
Links
Abstract
The present invention relates to a kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable, the preparation method includes the following steps: that mixed dissolution obtains mixed solution according to a certain ratio by zirconates, yttrium salt, dispersing agent；Mixed solution is heated up and carries out hydro-thermal reaction, adjusts the H of solution by the way that ammonium hydroxide or acid solution is added in water-heat process+Concentration is cooled to 90 DEG C hereinafter, obtaining hydrous zirconium oxide(HZO) suspension after fully reacting；Ammonium hydroxide is added into zirconia nanosuspensions to adjust pH to alkalinity, still aging, centrifuge separation obtains zirconium oxide precipitating；Zirconium oxide precipitating is subjected to a series of aftertreatment technologies and obtains the stable Zirconium oxide powder of nanometer yttrium.The above method is easy to control product pattern, granularity, crystal phase, simple to operate, is suitable for plant produced.
Description
Technical field
The present invention relates to material science and technology fields, steady more particularly, to a kind of nanometer yttrium that monodisperse granularity is controllable
Fixed Zirconium oxide powder and its preparation method and application.
Background technique
Zirconia ceramics is known as being only second to the second largest metal oxide ceramic of aluminium oxide ceramics, the main original of production
Material is Zirconium powder.Combined oxidation zirconium powder is nontoxic, tasteless white powder, has powder tiny, chemical uniformity is good
And easy to form, the characteristics such as sintering, it is mainly used in all kinds of structural ceramics, electronic ceramics, sensitive ceramic, bioceramic, advanced
In the industries such as refractory material, mechanical part, cutting element, watchcase, fibre-optical splice, solid oxygen fuel cell, have high-intensitive, high
Fracture toughness, it is corrosion-resistant, wear-resistant, anti-pollution the features such as.
If zirconium oxide composite material will be widely used, it is necessary to ensure low-porosity, high density, high intensity, height
The performances such as toughness.Other than physical and chemical performance and phase structure, prepared powder will also meet the requirement of different purposes, such as powder
Last crystal phase composition, average grain diameter, dispersibility, particle diameter distribution, specific surface area and porosity etc., these characteristics will all directly affect pottery
The performance parameter of porcelain, wherein being formed especially with crystal phase, granularity, size distribution are on the huge using influencing of nanometer yttrium stable zirconium oxide powder
Greatly, it because zirconia ceramics has a wide range of applications, but is different using the requirement to each performance parameter of nano oxidized zirconium powder
Difference, such as zirconium oxide for structural ceramics require it just to need the zirconia powder of full tetragonal phase with excellent performance, because
It is best for the zirconia ceramics comprehensive mechanical property of full tetragonal phase, but it is used for the zirconia ceramics of mobile phone backboard, it may be tough to its
Property require higher, this nano oxidized zirconium powder for just needing that there is tetragonal phase, monoclinic phase mixing crystal form.
The common preparation method of nanometer yttrium stable zirconium oxide powder has chemical coprecipitation, sol-gal process, hydro-thermal method at present
Deng.The precipitation method prepare Zirconium oxide powder, are in the solution to be sufficiently mixed zirconates and stabilizer etc., are made by dropwise addition precipitating reagent molten
The form for driving object in liquid before cation is precipitated from solution, then it is aged, the acquisitions such as to be filtered, washed, dry, calcining corresponding
Zirconium oxide powder.Coprecipitation process is simple, process is easily-controllable, cost is relatively low and sediment chemical constituent is uniformly mixed, and is system
The standby most common method of oxide powder.But during co-precipitation, pH value, anion, temperature etc. are to metal cation
Coordination, hydrolysis and polymerization process suffer from very big influence, so relatively be difficult to control product size, pattern and chemical group
At etc., and the powder diameter of precipitation method preparation is small, reunites serious and then influences properties of product.Sol-gal process can be in mild item
It is carried out under part, with reaction temperature is low, product grain is small, be evenly distributed, with high purity, constituent is easily controllable, controllable drilling
The advantages that porosity, but there is also some problems, and if sol-gal process is long reaction time, cost of material is high, and organic solvent is to human body
There is certain harmfulness etc., and there are a large amount of micropores in gel, causes to have remaining carbon after being heat-treated, dried
Cheng Zhonghui escapes many gases and organic matter and generates contraction, therefore is further improved.Furthermore during heat treatment, by
It is big in its specific surface, it is easy to reunite hardened；And this method production capacity is small, needs strict control process conditions, expensive raw material price, no
It is suitable for large-scale industrial production.
Summary of the invention
Based on this, it is an object of the invention to provide a kind of crystal phases, the controllable dispersed nano yttrium stable zirconium oxide powder of granularity
The preparation method at end, solves precursor preparation system complexity in existing preparation nanometer yttrium stable zirconium oxide powder technology, product pattern,
The technical problem that crystal phase and granularity are difficult to control.It is simple using technical solution of the present invention hydro-thermal hydrolyzation system, it is easy to control production
Product pattern, granularity, crystal phase, it is simple to operate, it is suitable for plant produced.
Hydro-thermal Hydrolyze method is to make inorganic zirconium salts solution spontaneous hydrolysis under hydrothermal condition of the temperature greater than 100 DEG C, prepare oxygen
Change the method for zirconium powder.The method had not only overcome the too long deficiency of water at atmospheric pressure solution reaction time consumption, but also remained its pattern and be easy to control
The advantages of processed.Basic zirconium chloride hydrolyzes equation in the solution are as follows:
ZrOCl2+(n+1)H2O→ZrO2·nH2O+2HCl
The apparent particle of hydro-thermal Hydrolyze method preparation is a kind of zirconium oxide with the crystallization water, generally also known as aqua oxidation
Zirconium.
A kind of preparation method for the Zirconium oxide powder that the nanometer yttrium that monodisperse granularity is controllable is stable, includes the following steps:
(1) by zirconates, yttrium salt, dispersing agent, mixed dissolution obtains mixed solution according to a certain ratio；
(2) mixed solution is heated up and carries out hydro-thermal reaction, adjust solution by the way that ammonium hydroxide or acid solution is added in water-heat process
H+, 90 DEG C are cooled to after fully reacting hereinafter, obtaining hydrous zirconium oxide(HZO) suspension；
(3) ammonium hydroxide is added in Xiang Suoshu hydrous zirconium oxide(HZO) suspension to adjust pH to alkalinity, still aging, centrifuge separation,
Obtain hydrous zirconium oxide(HZO) precipitating；
(4) hydrous zirconium oxide(HZO) precipitating washed, dried, calcination processing, Zirconium oxide powder is obtained, by zirconia powder
Ball milling after end, deionized water and dispersant, obtains slurry, and slurry grinding, centrifuge separation, washing and drying obtain
The stable Zirconium oxide powder of the nanometer yttrium controllable to monodisperse granularity.
The zirconium concentration in zirconates is 0.1-2.5mol/L, Zr in one of the embodiments,4+With Y3+Molar concentration rate
For 99:2-90:20, dispersant concentration 1g/L.
In one of the embodiments, in step (2), the mixed liquor is mixed with the revolving speed of 300-10000r/min,
The speed that lye or acid solution are added is 1-10000mL/min, wherein the concentration of ammonium hydroxide is 0.5-6mol/L, and the concentration of acid solution is
0.1-3mol/L。
The time of the hydro-thermal reaction is 3-20h in one of the embodiments,.
In one of the embodiments, in the step (3), temperature be 25 DEG C -90 DEG C, mixing speed 300-
Under conditions of 1000r/min, ammonium hydroxide is added into the hydrous zirconium oxide(HZO) suspension with the speed of 5-5000mL/min to adjust
PH to 8-14, still aging 6-24h.
In one of the embodiments, in step (4), washing includes washing and ethyl alcohol cleaning, the number of the washing
It is 3-7 times, the number of the ethyl alcohol cleaning is 1-3 times.
It is precipitated in one of the embodiments, in hydrous zirconium oxide(HZO) and is washed, dried, in calcination processing, the drying
Temperature be 50-80 DEG C, time of the drying is 10-14h, and the temperature of the calcining is 500-1300 DEG C, the calcining
Time is 1-3h.
The solid content ratio of slurry is 10%-30% in one of the embodiments, and the percentage that dispersing agent is added is
0.1%-0.5%.
Material ball ratio is 1:5-1:15 in one of the embodiments,.
The revolving speed of the ball milling is 30-90r/min, time 6-12h in one of the embodiments,；The revolving speed of grinding
For 2000-4000r/min, charging rate 20-100mL/min, time 30-120min.
In one of the embodiments, in slurry grinding, centrifugation, washing and drying, dry temperature is 50-80
DEG C, the dry time is 10-14h.
The present invention also provides the zirconium oxides that the controllable nanometer yttrium of monodisperse granularity made from the preparation method is stable
Powder.
The present invention also provides application of the Zirconium oxide powder in ceramic system is standby.
Compared with prior art, the present invention having the advantage that
(1) for the present invention compared with conventional hydrothermal method, present invention process is simple, low in cost, is conducive to industrialization.In existing skill
In the zirconium source settling step of art, the hydro-thermal presoma-a large amount of moisture of gel adsorption, and be extremely difficult to handle, this will cause ingredient
It is inhomogenous, and complex operation can be made, it is unfavorable for industrialized production, and the present invention passes through ammonium hydroxide and pickle to zirconium salt solution
Reaction is hydrolyzed, the additional amount of ammonium hydroxide is controlled in hydrolysis, because without generating a large amount of gel.Traditional hydro-thermal
Process needs more than for 24 hours；In supercritical water thermal process, for hydrothermal temperature at 400~500 DEG C, the requirement to equipment is high, above-mentioned
Two kinds of techniques, which all exist, is difficult to industrialized problem, and concentration of the present invention is applied widely, hydrolysis step and hydro-thermal reaction step
Rapid mild condition is very beneficial to industrialize.
(2) compared with the prior art, also having can be by adjusting the final H of reaction solution by the present invention+Concentration is realized most
The granularity of whole nanometer yttrium stable zirconium oxide powder is controllable, i.e., the nanometer yttrium of different-grain diameter is synthesized according to the different application demand of zirconates
Stabilized zirconia powders, this has very great meaning to the popularization and application of nanometer yttrium stable zirconium oxide powder.
(3) the crystal phase composition that can be realized nanometer yttrium stable zirconium oxide powder through the invention is controllable, according to the literature, oxygen
Change the performance of zircon ceramic and its crystal phase forms closely related, the nanometer yttrium stable zirconium oxide powder crystal phase composition of present invention process synthesis
It controllably can adapt to the types of applications of zirconia ceramics.
The dispersing agent being added in hydro-thermal hydrolytic process of the present invention is composite dispersing agent, it is a kind of the compound of organic and inorganic
Dispersing agent finds that it has better dispersion effect, dispersion relative to single organic or inorganic dispersant through overtesting
Mechanism has the following:
(1) the Organic-inorganic composite dispersing agent makes disperse system Thermodynamically stable in electrostatic stabilization, Mechanical instability；
(2) composite dispersing agent has adsorptivity to particle, and dispersing agent has very long space structure, that is, has sky
Between steric hindrance；
(3) reaction process not will lead to heterogeneous forming core phenomenon generation under dispersion effect.
Detailed description of the invention
Fig. 1 is the dispersing agent hydroxypropyl methyl cellulose structural formula that the present invention uses；
Fig. 2 is the pentasodium triphosphate of dispersing agent structural formula that the present invention uses；
Fig. 3 is a kind of process of the preparation method of nanometer yttrium stable zirconium oxide powder that monodisperse granularity is controllable of the invention
Figure；
Fig. 4 is the TEM figure of gained nanometer yttrium stable zirconium oxide powder after the embodiment of the present invention 1 is calcined；
Fig. 5 is the TEM figure of gained nanometer yttrium stable zirconium oxide powder after the embodiment of the present invention 2 is calcined；
Fig. 6 is the TEM figure of gained nanometer yttrium stable zirconium oxide powder after the embodiment of the present invention 3 is calcined；
Fig. 7 is the XRD diagram of nanometer yttrium stable zirconium oxide powder prepared by embodiment 4,5,6.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation,
It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.In addition, term " first ", " second ",
" third " is used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
A kind of preparation method for the nanometer yttrium stable zirconium oxide powder that monodisperse granularity is controllable, the preparation method include with
Lower step:
(1) zirconium oxychloride, yttrium chloride, dispersing agent material solution, Zr reaction solution preparation method: are prepared4+With Y3+It is mole dense
Degree ratio is 99:2~90:20；
(2) hydro-thermal hydrolysis process: the stainless steel that reaction solution obtained by step (1) is transferred to teflon lined is homogeneous
In reaction kettle, it is warming up to 120~300 DEG C of progress 3~20h of hydro-thermal reaction, during the reaction, 300~10000r/ of high-speed stirred
Under the conditions of min, by atomizer with 1~10000mL/min be added concentration be 0.5~6mol/L ammonia spirit or 0.1~
3mol/L acid solution solution adjusts material solution H+Concentration, so that Zr in solution4+Partial hydrolysis generates nucleus, adjusts Solution H+Concentration
Nucleus amount, its Zr after the completion of adjusting are generated for 0.1~5mol/L to control hydrolysis4+0.1~2.5mol/L of concentration, dispersant concentration
For 0.5~5g/L, crystal grain is grown up on the basis of nucleus, obtains spherical hydrous zirconia particles, and hydro-thermal reaction is completed, taken
Hydrothermal reaction kettle is cooled to 90 DEG C hereinafter, obtaining hydrous zirconium oxide(HZO) suspension out；
(3) the heavy yttrium technique of spatial induction: by above-mentioned hydrous zirconium oxide(HZO) suspension, in 25~90 DEG C of temperature, high-speed stirred
Under the conditions of 300~1000r/min, 0.5~6mol/L ammonia spirit, which is added, with 5~50mL/min by atomizer makes Y3+With hydrogen
The form of yttrium oxide is uniformly deposited in the surface of hydrous zirconium oxide(HZO), makes hydrous zirconium oxide(HZO) pH of suspension 8~14, and the yttrium that sinks reacts
Complete heavy yttrium after the reaction was completed, static ageing 6~for 24 hours, suspension is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment；
(4) aftertreatment technology: by (3) described sediment through washing 3~7 times, alcohol wash 1~3 time, centrifuge separation be placed on
10~14h is dried in baking oven at 50~80 DEG C, 1~3h is calcined at 500~1300 DEG C.Will calcining after powder, deionized water,
Dispersing agent (acid polyethylene ammonium) presses solid content 10%~30%, pellet mass ratio 1:5~1:15, dispersing agent 0.1%~0.5%
(percentage of powder quality) is uniformly mixed, and in general milling machine, 6~12h of ball milling is mixed at 30~90r/min of revolving speed
Uniform slurry is closed, then through fine grinding machine, is ground under the conditions of 2000~4000r/min of revolving speed, 20~100mL/min of charging rate
After grinding 30~120min, centrifugation alcohol is washed 1~3 time, and it is steady to obtain crystal phase granularity controllable nano yttrium by dry 10~14h at 50~80 DEG C
Determine Zirconium oxide powder.
In order to help to further understand the present invention, technical solution of the present invention is carried out now in conjunction with preferred embodiment detailed
Explanation.
Embodiment 1
(1) ZrOCl is prepared2、YCl3, dispersant solution, wherein hydroxypropyl methyl cellulose, hydroxypropyl cellulose,
Sodium tripolyphosphate equal proportion composition, Zr4+:Y3+Molar ratio is 97:6；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, in hydro-thermal hydrolytic process, under 500r/min stirring, by the way that 3.85mol/L dilute ammonia solution tune is added
Save the H of end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is 0.1mol/L, and dispersant concentration is
Cooling obtains hydrous zirconium oxide(HZO) suspension after 1g/L, reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension under the conditions of 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes
Y3+It uniformly is deposited in hydrous zirconia particles surface, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid,
Suspension is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment by static ageing 12h；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, acid polyethylene ammonium press solid content 30%, pellet mass ratio after calcining
1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling 6h
Uniformly mixed slurry is obtained, then through fine grinding machine, is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 2
(1) ZrOCl is prepared2、YCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 97:6；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, in hydro-thermal hydrolytic process, under 500r/min stirring, by the way that 3.15mol/L dilute ammonia solution tune is added
Save the H of end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is 0.3mol/L, hydroxypropyl cellulose
Concentration is 1g/L, and cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+Uniformly
Be deposited in hydrous zirconia particles surface, when pH of suspension > 9 stops that ammonium hydroxide is added, obtain heavy yttrium rear suspension liquid, it is static old
Change 12h, suspension is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifuged to be placed in baking oven at 65 DEG C and dry 10h,
2h is calcined at 1000 DEG C.Will calcining after powder, deionized water, acid polyethylene ammonium by solid content 30%, pellet mass ratio 1:15,
Dispersing agent 0.1% (percentage of powder quality) is uniformly mixed, and in general milling machine, ball milling 6h is obtained at revolving speed 60r/min
Uniformly mixed slurry, then through fine grinding machine, 60min is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
Afterwards, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 3
(1) ZrOCl is prepared2、YCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 97:6；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, in hydro-thermal hydrolytic process, under 500r/min stirring, is adjusted by the way that 2.1mol/L dilute ammonia solution is added
The H of end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is 0.6mol/L, and hydroxypropyl cellulose is dense
Degree is 1g/L, and cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+Uniformly it is deposited in water
Zirconia particles surface is closed, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid, static ageing 12h will hang
Supernatant liquid is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, acid polyethylene ammonium press solid content 30%, pellet mass ratio after calcining
1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling 6h
Uniformly mixed slurry is obtained, then through fine grinding machine, is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
From Fig. 2,3 and 4 it can be seen that nanometer yttrium stable zirconium oxide partial size is gradually increased, i.e., the present invention can be realized a nanometer yttrium
The size tunable of stabilized zirconia powders synthesizes.
Embodiment 4
(1) ZrOCl is prepared2、YCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 98:4, solution
CZr 4+=0.5mol/L, H+Concentration is 1.0mol/L, and hydroxypropyl cellulose concentration is 1g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+Uniformly it is deposited in water
Zirconia particles surface is closed, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid, static ageing 12h will hang
Supernatant liquid is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, acid polyethylene ammonium press solid content 30%, pellet mass ratio after calcining
1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling 6h
Uniformly mixed slurry is obtained, then through fine grinding machine, is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 5
(1) ZrOCl is prepared2、YCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 97:6, solution
CZr 4+=0.5mol/L, H+Concentration is 1.0mol/L, and hydroxypropyl cellulose concentration is 1g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+Uniformly it is deposited in water
Zirconia particles surface is closed, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid, static ageing 12h will hang
Supernatant liquid is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, acid polyethylene ammonium press solid content 30%, pellet mass ratio after calcining
1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling 6h
Uniformly mixed slurry is obtained, then through fine grinding machine, is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 6
(1) ZrOCl is prepared2、YCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 92:16, solution
CZr 4+=0.5mol/L, H+Concentration is that 1.0mol/L hydroxypropyl cellulose concentration is 1g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+Uniformly it is deposited in water
Zirconia particles surface is closed, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid, static ageing 12h will hang
Supernatant liquid is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, acid polyethylene ammonium press solid content 30%, pellet mass ratio after calcining
1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling 6h
Uniformly mixed slurry is obtained, then through fine grinding machine, is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 7
(1) ZrCl is prepared4、YCl3, hydroxypropyl methyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 97:6；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, in hydro-thermal hydrolytic process, under 500r/min stirring, is adjusted by the way that 2.1mol/L dilute hydrochloric acid solution is added
The H of end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is 1.8mol/L, hydroxypropyl methyl fiber
Plain concentration is 1g/L, and cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension under the conditions of 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes
Y3+It uniformly is deposited in hydrous zirconia particles surface, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid,
Suspension is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment by static ageing 12h；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, acid polyethylene ammonium press solid content 30%, pellet mass ratio after calcining
1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling 6h
Uniformly mixed slurry is obtained, then through fine grinding machine, is ground under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 8
(1) Zr (NO is prepared3)4、Y(NO3)3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+Molar ratio is 97:6；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, in hydro-thermal hydrolytic process, under 500r/min stirring, is adjusted by the way that 2.1mol/L dilute nitric acid solution is added
The H of end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is 1.8mol/L, and hydroxypropyl cellulose is dense
Degree is 1g/L, and cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension under the conditions of 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes
Y3+It uniformly is deposited in hydrous zirconia particles surface, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid,
Suspension is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment by static ageing 12h；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, Macrogol 6000 press solid content 30%, pellet quality after calcining
Than 1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball milling
6h obtains uniformly mixed slurry, then through fine grinding machine, grinds under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After grinding 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Embodiment 9
(1) Zr (SO is prepared4)2、Y(NO3)3, sodium tripolyphosphate mixed solution, wherein Zr4+:Y3+Molar ratio is 97:6；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, in hydro-thermal hydrolytic process, under 500r/min stirring, by the way that 1.05mol/L dilution heat of sulfuric acid tune is added
Save the H of end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is 1.8mol/L, and sodium tripolyphosphate is dense
Degree is 1g/L, and cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension under the conditions of 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes
Y3+It uniformly is deposited in hydrous zirconia particles surface, when the stopping addition ammonium hydroxide of pH of suspension > 9, obtains heavy yttrium rear suspension liquid,
Suspension is centrifugally separating to obtain hydrous zirconium oxide(HZO) sediment by static ageing 12h；
(4) (3) described sediment washed 2 times through washing 5 times, alcohol, be centrifugated to be placed in baking oven and dried at 65 DEG C
10h calcines 2h at 1000 DEG C.Powder, deionized water, dodecyl sodium sulfate press solid content 30%, pellet matter after calcining
Amount than 1:15, dispersing agent 0.1% (percentage of powder quality) be uniformly mixed, in general milling machine at revolving speed 60r/min ball
Mill 6h obtains uniformly mixed slurry, then through fine grinding machine, under the conditions of revolving speed 3000r/min, charging rate 50mL/min
After grinding 60min, centrifugation alcohol is washed 2 times, and dry 10h obtains crystal phase granularity controllable nano yttrium stable zirconium oxide powder at 65 DEG C.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method for the Zirconium oxide powder that the nanometer yttrium that monodisperse granularity is controllable is stable, which is characterized in that including such as
Lower step:
(1) by zirconates, yttrium salt, dispersing agent, mixed dissolution obtains mixed solution according to a certain ratio, wherein the dispersing agent includes hydroxyl
Propyl methocel, hydroxypropyl cellulose, sodium tripolyphosphate it is one or more；
(2) mixed solution is heated up and carries out hydro-thermal reaction, adjust the H of solution by the way that ammonium hydroxide or acid solution is added in water-heat process+,
90 DEG C are cooled to after fully reacting hereinafter, obtaining hydrous zirconium oxide(HZO) suspension；
(3) ammonium hydroxide is added in Xiang Suoshu hydrous zirconium oxide(HZO) suspension to adjust pH to alkalinity, still aging, centrifuge separation obtains
Hydrous zirconium oxide(HZO) precipitating；
(4) hydrous zirconium oxide(HZO) precipitating washed, dried, calcination processing, nano zirconium oxide powder is obtained, by nano zircite
Ball milling after powder, deionized water and dispersant, obtains slurry, then by slurry carry out fine gtinding, centrifuge separation, washing and
It is dry, obtain the stable Zirconium oxide powder of the controllable nanometer yttrium of monodisperse granularity.
2. the method according to claim 1, wherein the zirconates includes zirconium oxychloride, zirconium nitrate, zirconium sulfate,
Preferably zirconium oxychloride；Yttrium salt includes yttrium chloride, yttrium nitrate, preferably yttrium chloride；The acid solution includes hydrochloric acid, nitric acid, sulfuric acid,
Preferably hydrochloric acid；Zirconium concentration in the zirconates is 0.1-2.5mol/L, Zr4+And Y3+Molar concentration rate be 99:2-90:20,
Dispersant concentration is 0.5~5g/L.
3. preparation method according to claim 1, which is characterized in that in step (1), the mixed liquor is with 300-
The revolving speed of 10000r/min mixes, and the speed that ammonium hydroxide or acid solution are added is 1-10000mL/min, wherein the concentration of ammonium hydroxide is
0.5-6mol/L, the concentration of acid solution are 0.1-3mol/L.
4. preparation method according to claim 1, which is characterized in that in step (2), be warming up to 120 DEG C -300 DEG C, institute
The time for stating hydro-thermal reaction is 3-20h.
5. preparation method according to claim 1, which is characterized in that be 25 DEG C -90 in temperature in the step (3)
DEG C, under conditions of mixing speed is 300-1000r/min, with the speed of 5-5000mL/min to the hydrous zirconium oxide(HZO) suspension
Middle addition ammonium hydroxide adjusts pH to 8-14, still aging 6-24h；In step (4), washing includes washing and ethyl alcohol cleaning, institute
The number for stating washing is 3-7 times, and the number of the ethyl alcohol cleaning is 1-3 times.
6. preparation method according to claim 1, which is characterized in that precipitated in hydrous zirconium oxide(HZO) and washed, dried, forged
In burning processing, the temperature of the drying is 50-80 DEG C, and the time of the drying is 10-14h, and the temperature of the calcining is 500-
1300 DEG C, the time of the calcining is 1-3h.
7. preparation method according to claim 1, which is characterized in that in step 4, the dispersing agent includes acid polyethylene
Ammonium, Macrogol 6000, dodecyl sodium sulfate it is one or more, dispersing agent be added percentage be 0.1%-0.5%；Institute
Stating slurry solid content is 10%~30%, material ball ratio 1:5-1:15；The revolving speed of the ball milling is 30-90r/min, time 6-
12h；The revolving speed of fine gtinding is 2000-4000r/min, charging rate 20-100mL/min, time 30-120min.
8. preparation method according to claim 1, which is characterized in that in slurry grinding, centrifuge separation, washing and do
In dry, dry temperature is 50-80 DEG C, and the dry time is 10-14h.
9. the stable oxidation of the controllable nanometer yttrium of monodisperse granularity made from the described in any item preparation methods of claim 1 to 8
Zirconium powder.
10. application of the Zirconium oxide powder as claimed in claim 9 in ceramic system is standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910196936.9A CN109721357A (en) | 2019-03-15 | 2019-03-15 | A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910196936.9A CN109721357A (en) | 2019-03-15 | 2019-03-15 | A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109721357A true CN109721357A (en) | 2019-05-07 |
Family
ID=66302522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910196936.9A Pending CN109721357A (en) | 2019-03-15 | 2019-03-15 | A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109721357A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113372113A (en) * | 2021-07-01 | 2021-09-10 | 北京赛乐米克材料科技有限公司 | Preparation method of polycrystalline zirconium gem |
| CN114394830A (en) * | 2021-12-28 | 2022-04-26 | 中红外激光研究院(江苏)有限公司 | Preparation method of high-strength zirconia ceramic |
| CN115124074A (en) * | 2022-07-26 | 2022-09-30 | 宣城市晶纳环保科技有限公司 | Preparation method of high-dispersion composite nano zirconium dioxide |
| CN116161958A (en) * | 2022-12-27 | 2023-05-26 | 中铝广西有色稀土开发有限公司 | Preparation method of yttrium-stabilized zirconia nano-powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740246A (en) * | 1985-06-06 | 1988-04-26 | Remet Corporation | Casting of reactive metals into ceramic molds |
| CN101124166A (en) * | 2004-10-04 | 2008-02-13 | 布勒潘泰克有限公司 | Method for production of nanoparticles with custom surface chemistry and corresponding colloids |
| CN104725051A (en) * | 2015-02-25 | 2015-06-24 | 江苏金石研磨有限公司 | Preparation method of nano zirconia coated alumina powder |
| US20170189143A1 (en) * | 2015-12-07 | 2017-07-06 | Wdt-Wolz-Dental-Technik Gmbh | Process For The Production Of A Ceramic Body, In Particular Of A Dental Ceramic Blank, With Spatially Selectively Adjustable Degrees Of Physical Properties |
| CN107840658A (en) * | 2017-11-23 | 2018-03-27 | 华南理工大学 | A kind of preparation method of high-fracture toughness zirconia ceramics |
-
2019
- 2019-03-15 CN CN201910196936.9A patent/CN109721357A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740246A (en) * | 1985-06-06 | 1988-04-26 | Remet Corporation | Casting of reactive metals into ceramic molds |
| CN101124166A (en) * | 2004-10-04 | 2008-02-13 | 布勒潘泰克有限公司 | Method for production of nanoparticles with custom surface chemistry and corresponding colloids |
| CN104725051A (en) * | 2015-02-25 | 2015-06-24 | 江苏金石研磨有限公司 | Preparation method of nano zirconia coated alumina powder |
| US20170189143A1 (en) * | 2015-12-07 | 2017-07-06 | Wdt-Wolz-Dental-Technik Gmbh | Process For The Production Of A Ceramic Body, In Particular Of A Dental Ceramic Blank, With Spatially Selectively Adjustable Degrees Of Physical Properties |
| CN107840658A (en) * | 2017-11-23 | 2018-03-27 | 华南理工大学 | A kind of preparation method of high-fracture toughness zirconia ceramics |
Non-Patent Citations (2)
| Title |
|---|
| 刘志宏: "钇稳定四方相氧化锆粉末的水热水解法制备", 《中国有色金属学报》 * |
| 刘运飞: "建筑陶瓷用复合分散剂的制备与性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113372113A (en) * | 2021-07-01 | 2021-09-10 | 北京赛乐米克材料科技有限公司 | Preparation method of polycrystalline zirconium gem |
| CN114394830A (en) * | 2021-12-28 | 2022-04-26 | 中红外激光研究院(江苏)有限公司 | Preparation method of high-strength zirconia ceramic |
| CN115124074A (en) * | 2022-07-26 | 2022-09-30 | 宣城市晶纳环保科技有限公司 | Preparation method of high-dispersion composite nano zirconium dioxide |
| CN115124074B (en) * | 2022-07-26 | 2024-02-06 | 宣城市晶纳环保科技有限公司 | Preparation method of high-dispersion composite nano zirconium dioxide |
| CN116161958A (en) * | 2022-12-27 | 2023-05-26 | 中铝广西有色稀土开发有限公司 | Preparation method of yttrium-stabilized zirconia nano-powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109721357A (en) | A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable | |
| CN109704731B (en) | Preparation method of nano yttrium-stabilized zirconia-alumina composite powder | |
| CN102659149B (en) | Preparation method for monodisperse high-purity alpha-Al2O3 powder | |
| CN107151029B (en) | A kind of sol-gel self-combustion synthesis preparation process of tetra phase barium titanate powder | |
| CN103708831A (en) | Yttria-stabilized zirconia powder and preparation method thereof | |
| CN109704403B (en) | High-toughness zirconia-based composite powder and preparation method thereof | |
| CN100384738C (en) | Preparation method of ultrafine alpha-Al2O3 powder and obtained product | |
| CN104894636B (en) | The preparation method of eight potassium titanate crystal whiskers | |
| CN109704759A (en) | A kind of compound rare-earth modified zirconia ceramic powder and preparation method thereof | |
| CN113461051B (en) | Preparation method of nano zirconia powder | |
| CN106938931A (en) | High purity high dense yttrium stable zirconium oxide ceramics and preparation method thereof | |
| CN104829218A (en) | Bimodal active alumina micropowder and preparation method | |
| CN112745105B (en) | High-sintering-activity alumina ceramic powder and preparation method thereof | |
| CN112357955B (en) | Method for preparing titanium dioxide powder with different morphologies by solid phase method | |
| CN103588246A (en) | Preparation process for nano zirconia powder | |
| CN112897579A (en) | Yttrium-stabilized nano zirconia powder and preparation method thereof | |
| CN109678500A (en) | Yttrium stable zirconium oxide ceramic powders and its preparation method and application | |
| CN113200567A (en) | High-sintering-activity zirconium oxide powder and preparation method thereof | |
| CN114133240B (en) | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method | |
| CN110713206A (en) | Preparation method of indium oxide-copper oxide composite material | |
| CN110078120A (en) | A kind of preparation method of the yttria-stabilized zirconia powder based on supercritical dispersion roasting | |
| CN110015889A (en) | A kind of ZTA ceramic material preparation method and its material of preparation | |
| CN108609652A (en) | A method of preparing Zirconium dioxide nano powder using fused salt | |
| CN1168785C (en) | Process for preparing nano zirconium oxide powder | |
| CN108083334A (en) | A kind of preparation method of monodisperse spherical nano zirconium dioxide powder body material |
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 |