CN107364884B - A kind of nano zirconium oxide powder preparation method - Google Patents
A kind of nano zirconium oxide powder preparation method Download PDFInfo
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention relates to a kind of nano zirconium oxide powder preparation methods, the technical solution avoids the problems such as calcination temperature present in traditional co-precipitation method is high, Ball-milling Time is long, hard agglomeration size is big, nano zirconium oxide powder is prepared using this method, good dispersion, hard agglomeration size is small.
Description
Technical field
The present invention relates to a kind of preparation methods, and in particular to a kind of preparation method of nano zirconium oxide powder belongs to ceramics
Powder preparation technical field.
Background technique
Zirconium oxide is because of its unique transformation toughening effect, therefore the intensity and toughness for example high with excellent mechanical property
Deng.Zirconium oxide has low thermal conductivity, high oxonium ion permeability and good biocompatibility simultaneously, is widely used in tying
Structure ceramic, high temperature thermal insulation coating, lambda sensor, tooth and joint prosthesis etc..
According to temperature difference, zirconium oxide has monocline, four directions and cube three kinds of different phase structures.Zirconium oxide is at room temperature
Monoclinic phase, tetragonal phase is converted at 1100 DEG C or so, and tetragonal phase is converted into cubic phase at 2300 DEG C or so.Due to tetragonal zircite
With optimal mechanical property, usually in the preparation, using a certain amount of phase stabiliser is added, (the most commonly used is yttrium oxide, contents
For the method for 3mol%), tetragonal phase is stablized to room temperature, to guarantee the optimum performance of product.
For zirconia ceramics due to fusing point height, brittleness is big, mostly uses powder base and the mode of solid-phase sintering is combined to form.For
The optimal mechanical property of acquisition, needs for the density of product to be sintered to close to its theoretical value.The sintering activity of powder is to determine
Zirconia ceramics sinterability can be with the core of final performance.When the sintering activity of powder is low, generally require in higher temperature
Degree is lower to be sintered, not only high production cost, while being also resulted in the burning of product part and being scrapped.Improve the sintering activity of powder
Sintering temperature can be not only reduced, while can also promote properties of product and qualification rate.
The existing main method for improving Zirconium oxide powder sintering activity is to reduce its crystallite dimension.It is hard when not contained in powder
When reunion, the crystallite dimension of powder is smaller, and specific surface area is bigger, and sintering activity is higher.Some researches show that when powder
Crystallite dimension is reduced within 100nm from micron order, and in powder hard agglomeration size it is small or be free of hard agglomeration when, oxygen
The sintering temperature for changing zircon ceramic can be down within 1200 DEG C from 1600 DEG C or more.Simultaneously because crystal grain refinement, ceramic bending
Intensity, fracture toughness etc. are obviously improved.Therefore, hard aggregation-free body or the small high-performance nano zirconium oxide of hard agglomeration size
The technology of preparing of powder is all the hot spot of zirconia ceramics area research all the time.
The preparation method of existing nano zirconium oxide powder mainly have Hydrolyze method, coprecipitation, sol-gal process, hydro-thermal method,
Vapor phase method etc., every kind of preparation method have advantage and disadvantage.Such as Hydrolyze method, the process time is long, and energy consumption is high, corrodes to equipment big；It is molten
The raw material of sol-gel are expensive；Hydro-thermal method and vapor phase method equipment investment are big, single heat low output etc..In comparison, it is co-precipitated
The advantages that method has the prices of raw materials low, and process equipment is simple, and single heat yield is high, is widely used at present.
The basic principle of coprecipitation is to use alkaline precipitating agent that zirconium ion is precipitated in the form of zirconium hydroxide, so
Zirconium hydroxide is calcined to slough hydroxyl between 1000-1100 DEG C afterwards, it is made to be converted into zirconium oxide.Due to have passed through height
Warm process, there are a large amount of large scale hard agglomerations in the nano zircite formed after calcining.In order to eliminate hard agglomeration or subtract
The size of small hard agglomeration needs that dispersing agent is added in the stages such as precipitating, washing and ball millings.But existed based on ball milling to diameter
The dispersibility of several hundred nanometers of hard agglomeration is low, and required Ball-milling Time is long and can not fully open hard agglomeration.Using this
Class powder preparation zirconia ceramics, sintering temperature cannot not only be effectively reduced, simultaneously because the defects of there are gross blow holes and it is difficult
To obtain high extrudate density.Therefore, a kind of new scheme of urgent need solves the technical problem.
Summary of the invention
The present invention exactly aiming at the problems existing in the prior art, provides a kind of nano zirconium oxide powder preparation method, should
Technical solution avoids the problems such as calcination temperature present in traditional co-precipitation method is high, Ball-milling Time is long, hard agglomeration size is big,
Nano zirconium oxide powder is prepared using this method, good dispersion, hard agglomeration size is small.
To achieve the goals above, technical scheme is as follows, a kind of preparation method of nano zirconium oxide powder, institute
State method the following steps are included:
Step 1: deionized water dissolving is added in water soluble zirconium salt and yttrium salt, and two solution are uniformly mixed, is mixed
Solution.Wherein, ruthenium ion content (Y3+/(Zr4++Y3+)) between (2 ~ 4) mol%；
Step 2: preparing alkaline sedimentation agent solution, and mixed solution prepared by step 1 is slowly dropped to alkaline sedimentation
In agent solution, it is stirred continuously during being added dropwise；Successively sediment is filtered and is dried again, obtains solid mixture；
Step 3: after solid mixture described in step 2 is calcined 2 ~ 5 hours between 800 DEG C ~ 900 DEG C；Naturally it drops
When temperature is between 100 ~ 300 DEG C, it is passed through vapor and carries out gas steaming, keep pressure between 0.5 ~ 10MPa, after gas steams 1 ~ 10 hour
Cooled to room temperature；
Step 4: water and dispersing agent is added in product described in step 3, ball milling is carried out, Ball-milling Time is 1 ~ 10 small
When；
Step 5: slurry after ball milling described in step 4 to be filtered, washed and dried to get nano oxidized zirconium powder
End.Wherein, washing uses the aqueous solution of ethyl alcohol, and the ratio between ethyl alcohol and water are (2.5 ~ 3): 1.
As an improvement of the present invention, alkaline precipitating agent described in step 2 is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
The concentration of solution is (2 ~ 10) mol% after addition.
As an improvement of the present invention, dispersing agent described in the step 4 is polyacrylic acid or its ammonium salt, is added
Amount is (0.5 ~ 5) % of Zirconium oxide powder weight.
It compared with the existing technology, can the present invention has the advantage that steaming link by increasing gas during the preparation process
Obtain the product of more dominance energy.Its technical principle is as follows: in existing chemical coprecipitation technique, zirconium hydroxide is in calcination process because de-
Hydroxyl is removed, produces zirconium oxygen zirconium key and hydrogen bond etc. between particles, is the core that there is the hard agglomeration for being difficult to disperse in powder
Reason, hard agglomeration is extremely difficult to be dispersed by modes such as ball millings.It is a large amount of studies have shown that zirconium oxide between room temperature ~ 600 DEG C,
In the presence of having water, " low temperature aging " effect can occur for zirconium oxide namely zirconia ceramics will appear cracking or dusting.It makes
Possible cause at this phenomenon is that hydroxide ion enters in the lattice of tetragonal zircite, makes distortion of lattice and generates stress,
Lead to grain boundary separation；Also theory is considered that zirconium surface characteristic changes.The technical program exactly utilizes zirconium oxide
This feature increases gas and steams work step, and the zirconium oxygen zirconium key in the hard agglomeration generated when powder is calcined destroys, and reduces hard agglomeration
Size, then promote by ball milling and dispersing agent the dispersibility of powder.Studies have shown that the pressure between 100 DEG C ~ 300 DEG C
Under environment, the fastest of " low temperature aging " occurs for zirconium oxide, therefore selects to carry out gas steaming in the temperature range, can be improved
" aging speed ", improving production efficiency.
Although the technical solution, which increases gas, steams work step, since initial calcination temperature is only 800 DEG C ~ 900 DEG C, with tradition
Coprecipitation between 1000 DEG C ~ 1100 DEG C to powder carry out calcining compare, do not obviously increase cost on the whole.Together
When, since hard agglomeration quantity and size are greatly decreased in powder, drop the sintering temperature of subsequent ceramics and rejection rate also obviously
Low, benefit is evident for overall cost.
Specific embodiment:
In order to deepen the understanding of the present invention, it is described in detail below with reference to embodiment.
Embodiment 1: a kind of preparation method of nano zirconium oxide powder powder the described method comprises the following steps:
Step 1: deionized water dissolving is added in zirconium oxychloride and yttrium chloride, and two solution are uniformly mixed, is mixed
Solution, wherein ruthenium ion content (Y3+/(Zr4++Y3+)) it is 2.5mol%；
Step 2: compound concentration is the NaOH solution of 3mol/L, and mixed solution prepared by step 1 is slowly dropped to
It in NaOH solution, is stirred continuously during dropwise addition, after being added dropwise to complete, sediment is filtered and is dried, it is mixed to obtain solid
Close object；
Step 3: after solid mixture described in step 2 is calcined 5 hours at 850 DEG C；When being cooled to 180 DEG C,
Vapor is passed through in furnace, holding pressure is 1.2MPa, and it is cooled to room temperature after 5 hours that gas, which steams,；
Step 4: water and ammonium polyacrylate is added in product described in step 3, wherein ammonium polyacrylate amount be added
It is the 2% of Zirconium oxide powder weight, ball milling 5 hours；
Step 5: after slurry after ball milling described in step 4 is filtered, using ethanol solution (the ratio between second alcohol and water
After being washed 5 times repeatedly for 3:1), dry at 110 DEG C to get nano zirconium oxide powder.
Embodiment 2: a kind of preparation method of nano zirconium oxide powder powder the described method comprises the following steps:
Step 1: deionized water dissolving is added in zirconium oxychloride and yttrium chloride, and two solution are uniformly mixed, is mixed
Solution, wherein ruthenium ion content (Y3+/(Zr4++Y3+)) it is 3mol%；
Step 2: compound concentration is the NaOH solution of 5mol/L, and mixed solution prepared by step 1 is slowly dropped to
It in NaOH solution, is stirred continuously during dropwise addition, after being added dropwise to complete, sediment is filtered and is dried, it is mixed to obtain solid
Close object；
Step 3: after solid mixture described in step 2 is calcined 5 hours at 800 DEG C；When being cooled to 120 DEG C,
Vapor is passed through in furnace, holding pressure is 0.6MPa, and it is cooled to room temperature after 8 hours that gas, which steams,；
Step 4: water and ammonium polyacrylate is added in product described in step 3, wherein ammonium polyacrylate amount be added
It is the 4% of Zirconium oxide powder weight, ball milling 6 hours；
Step 5: after slurry after ball milling described in step 4 is filtered, using ethanol solution (the ratio between second alcohol and water
After being washed 5 times repeatedly for 2.8:1), dry at 110 DEG C to get nano zirconium oxide powder.
Embodiment 3: a kind of preparation method of nano zirconium oxide powder powder the described method comprises the following steps:
Step 1: deionized water dissolving is added in zirconium oxychloride and yttrium chloride, and two solution are uniformly mixed, is mixed
Solution, wherein ruthenium ion content (Y3+/(Zr4++Y3+)) it is 3.5mol%；
Step 2: compound concentration is the NaOH solution of 8mol/L, and mixed solution prepared by step 1 is slowly dropped to
It in NaOH solution, is stirred continuously during dropwise addition, after being added dropwise to complete, sediment is filtered and is dried, it is mixed to obtain solid
Close object；
Step 3: after solid mixture described in step 2 is calcined 3 hours at 900 DEG C；When being cooled to 250 DEG C,
Vapor is passed through in furnace, holding pressure is 8MPa, and it is cooled to room temperature after 2 hours that gas, which steams,；
Step 4: water and ammonium polyacrylate is added in product described in step 3, wherein ammonium polyacrylate amount be added
It is the 2% of Zirconium oxide powder weight, ball milling 4 hours；
Step 5: after slurry after ball milling described in step 4 is filtered, using ethanol solution (the ratio between second alcohol and water
After being washed 5 times repeatedly for 3:1), dry at 110 DEG C to get nano zirconium oxide powder.
Embodiment 4: a kind of preparation method of nano zirconium oxide powder powder the described method comprises the following steps:
Step 1: deionized water dissolving is added in zirconium oxychloride and yttrium chloride, and two solution are uniformly mixed, is mixed
Solution, wherein ruthenium ion content (Y3+/(Zr4++Y3+)) it is 3.1mol%；
Step 2: compound concentration is the NaOH solution of 4mol/L, and mixed solution prepared by step 1 is slowly dropped to
It in NaOH solution, is stirred continuously during dropwise addition, after being added dropwise to complete, sediment is filtered and is dried, it is mixed to obtain solid
Close object；
Step 3: after solid mixture described in step 2 is calcined 3 hours at 880 DEG C；When being cooled to 210 DEG C,
Vapor is passed through in furnace, holding pressure is 1.7MPa, and it is cooled to room temperature after 4 hours that gas, which steams,；
Step 4: water and ammonium polyacrylate is added in product described in step 3, wherein ammonium polyacrylate amount be added
It is the 2.5% of Zirconium oxide powder weight, ball milling 4 hours；
Step 5: after slurry after ball milling described in step 4 is filtered, using ethanol solution (the ratio between second alcohol and water
After being washed 5 times repeatedly for 3:1), dry at 110 DEG C to get nano zirconium oxide powder.
Embodiment 5: a kind of preparation method of nano zirconium oxide powder powder the described method comprises the following steps:
Step 1: deionized water dissolving is added in zirconium oxychloride and yttrium chloride, and two solution are uniformly mixed, is mixed
Solution, wherein ruthenium ion content (Y3+/(Zr4++Y3+)) it is 3mol%；
Step 2: compound concentration is the NaOH solution of 6mol/L, and mixed solution prepared by step 1 is slowly dropped to
It in NaOH solution, is stirred continuously during dropwise addition, after being added dropwise to complete, sediment is filtered and is dried, it is mixed to obtain solid
Close object；
Step 3: after solid mixture described in step 2 is calcined 2 hours at 900 DEG C；When being cooled to 300 DEG C,
Vapor is passed through in furnace, holding pressure is 8.8MPa, and it is cooled to room temperature after 1 hour that gas, which steams,；
Step 4: water and ammonium polyacrylate is added in product described in step 3, wherein ammonium polyacrylate amount be added
It is the 4.5% of Zirconium oxide powder weight, ball milling 4 hours；
Step 5: after slurry after ball milling described in step 4 is filtered, using ethanol solution (the ratio between second alcohol and water
After being washed 5 times repeatedly for 3:1), dry at 110 DEG C to get nano zirconium oxide powder.
For contrast properties, powder is prepared using traditional precipitation method nano zircite, wherein Step 1: two with phase of the present invention
Together, step 3 is to calcine 2 hours at 1050 DEG C；Step 4 is ball milling 50 hours.You is allowed to obtain using laser particle analyzer test
Powder diameter is announced as shown in table 1, it can be seen that uses powder prepared by the present invention, Water-borne paint is obviously reduced.
The distribution of 1 two methods powder agglomerates size of table
。
It should be noted that above-described embodiment, is not intended to limit the scope of protection of the present invention, in above-mentioned technical proposal
On the basis of made equivalents or substitution each fall within the range that the claims in the present invention are protected.
Claims (3)
1. a kind of nano zirconium oxide powder preparation method, which is characterized in that the described method comprises the following steps: Step 1: by water
Deionized water dissolving is added in dissolubility zirconates and yttrium salt, and two solution are uniformly mixed, and obtains mixed solution；Wherein, ruthenium ion contains
Measure Y3+/(Zr4++Y3+) between (2 ~ 4) mol%；Step 2: preparing alkaline sedimentation agent solution, and mixing step 1 preparation
It closes solution to be slowly dropped in alkaline sedimentation agent solution, be stirred continuously during being added dropwise；Successively sediment is filtered again and
It is dry, obtain solid mixture；Step 3: it is small that solid mixture described in step 2 is calcined to 2 ~ 5 between 800 DEG C ~ 900 DEG C
Shi Hou；When being naturally cooling between 100 DEG C ~ 300 DEG C, it is passed through vapor and carries out gas steaming, keep pressure between 0.5-10MPa,
Cooled to room temperature after gas steams 1 ~ 10 hour；Step 4: water and dispersing agent is added in the product in step 3, ball milling is carried out,
Ball-milling Time is 1 ~ 10 hour；
Step 5: slurry after ball milling described in step 4 to be filtered, wash and dry to get nano zirconium oxide powder；
Wherein, washing uses the aqueous solution of ethyl alcohol, and the ratio between ethyl alcohol and water are (2.5 ~ 3): 1.
2. nano zirconium oxide powder preparation method according to claim 1, which is characterized in that alkalinity described in step 2 is heavy
Shallow lake agent is sodium hydroxide, potassium hydroxide or ammonium hydroxide, and concentration is (2 ~ 10) mol%.
3. nano zirconium oxide powder preparation method according to claim 2, which is characterized in that divide described in the step 4
Powder is polyacrylic acid or its ammonium salt, and additional amount is (0.5 ~ 5) % of Zirconium oxide powder weight.
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