CN102219534B - Method for preparing nano oxide slurry - Google Patents
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
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- 229920002125 Sokalan® Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to a method for preparing nano oxide slurry. The method for preparing the nano oxide slurry is characterized by comprising the following steps: preparing an acidic surface modifying agent solution and preparing the nano oxide slurry with the pH of 2-5 through one of methods A and B, wherein in the method A, the acidic surface modifying agent solution is added into dried nano oxide powder, and stirring is carried out while adding is carried out; in the method B, water is firstly added into the acidic surface modifying agent or acidic surface modifying agent solution for evenly stirring, and then the mixture is added to the nano oxide powder, and the stirring is carried out while adding is carried out; and in the method A or B, the weight ratio of the nano oxide powder to the water is (2:8)-(7:3). The nano oxide slurry has good flowability and good stability besides high solid content, is suitable for preparation of powder for a thermal spray process and a high temperature sintering process; and the preparation process is simple, convenient for operation, safe and reliable, low in cost and suitable for industrial production.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, be specifically related to a kind of preparation method of nano oxide slurry.
Background technology
Along with the development of maturation and the hot spray coating technology of nanosecond science and technology and nano-powder technology of preparing, the preparation of the coating of nanostructure has realized suitability for industrialized production.Utilize the nanostructured thermal barrier coatings of nanotechnology exploitation to refer to that the microstructure of thermal barrier coating such as crystal grain, hole etc. are in nanometer level (2-100nm), thereby mechanics and physicals to coating produce material impact, can obtain the performance more excellent than ordinary hot barrier coating.
The key of preparation nanostructured thermal barrier coatings is that the nanostructure micron-size spherical powder that thermospray requires is satisfied in preparation at present.The used for hot spraying nanometer powder requires it inner must keep nanostructure, and satisfies the spraying coating process requirement, as granular size and distribution thereof, particle shape, mobility etc.During thermospray, only have particle just can possess the required quality of plasma spraying when a certain size and density, granular mass is too little, can not obtain enough kinetic energy, and spray is less than workpiece surface.And nano-powder self mobility extreme difference, directly use can not be satisfied the powder feeding requirement of spraying coating process, so nano-powder must be made the micron-size spherical dusty spray through mist projection granulating and densification process, then adopt the spraying coating process such as plasma spraying to be deposited as coating.
Used for hot spraying nanostructure micron-size spherical powder mainly adopts the spray-drying process preparation, spray-drying process is that nanometer oxide powder is mixed with a certain amount of binding agent, add appropriate water to be mixed with the slurry of certain solids content, adopt certain pressure with pulp jets in drying tower, the slurry droplet is dry in hot blast, is agglomerated into spherical by self surface tension.Be subjected to the restriction of present mist projection granulating equipment performance, in order to obtain the dry powder of certain particle size (as 20 μ m～90 μ m), must control the content of the solid powder in slurry, usually solid content 30%～70% the time, could can satisfy the micron-size spherical powder that sprays needs by centrifugal (or two fluids) spray granulating and drying technique acquisition grain graininess.
But the surface tissue that nanoparticle is little because of its particle diameter, specific surface area large, the surface can be high and special, be difficult to improve its solid content in preparation slurry process, when the solid content of nano-powder surpassed 30%, the mobility of slip is variation significantly, is difficult to mist projection granulating.Therefore, obtain having high solids content, the nano material slurry of high workability and stability is the key that successfully prepares nanostructure micron-size spherical powder.
The requirement of used for hot spraying nano oxide slurry mainly comprises following three aspects: the one, have high solid volume fraction, i.e. high solids content; The 2nd, have good mobility, namely have lower viscosity characteristics; The 3rd, have good uniform and stable property.High solid volume fraction and good mobility are that low viscosity is the conflict body, and solid volume fraction is higher usually, and the mobility of slurry is less.For nano-powder; because its grain diameter is little; specific surface area is large; specific surface energy is large; surfactivity is high; thereby in water medium; highly active powder granule can with the water molecules effect; make a large amount of free water be converted into water of constitution, thereby be difficult to make slurry to keep again good mobility when having high solid volume fraction, and when the solid volume fraction of slurry is very high; intergranular distance is less; the basic neutral of particle surface, interaction force is large, cohesion and flocculation very easily occur and loses the original special performance of ultra-fine grain.The surface modification of nano-powder is the Major Technology that people address this problem.
In addition, in the preparation process of nano-structural ceramic, due to the above-mentioned character of nano particle, cause the difficult forming of ceramic body, if first nanoparticle agglomerates is become micron-sized macrobead, also be conducive to reduce forming pressure, improve the compactness of pottery.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method for preparing nano oxide slurry.The nano oxide slurry that the method is produced also has good mobility when having high solids content, good stability is applicable to satisfy the preparation of nanostructure hot-spraying techniques and the needed micron order nano-oxide of high-sintering process spherical powder.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of method for preparing nano oxide slurry is characterized in that: comprise the following steps:
1) solution of the acid surface-modifying agent of preparation;
2) preparation pH is the nano oxide slurry of 2-5, and described pH is that the nano oxide slurry of 2-5 is by a kind of the preparing in following two kinds of methods:
Method A: the acidic surface modifier solution that step 1) is prepared joins in the dried shape thing of nano oxide powder, the limit edged stirs, until formation pH is 2～5 nano oxide slurry, the dried shape thing of described nano oxide powder obtains by add the entry stirring in nano oxide powder;
Method B: the acidic surface modifier solution of acidic surface properties-correcting agent or step 1) preparation first is added to the water, stirs, then join in nano oxide powder, the limit edged stirs, until formation pH is 2～5 nano oxide slurry; In described method A or method B, the weight ratio of nano oxide powder and water is 2:8～7:3.
Press such scheme, step 2) nano-oxide described in is one or more the mixing in yttrium stabilized nanoscale zirconium white, nano titanium oxide, nano aluminium oxide, nano silicon, nanometer cobalt oxide, nano-nickel oxide, and its diameter of particle is 3～100nm.
Press such scheme, the acidic surface properties-correcting agent described in step 1) is for being one or more the mixing in formic acid, acetic acid, polyacrylic acid, hydrochloric acid, nitric acid.
The nano oxide slurry solid content of the method preparation can reach 30～70%, and the nano oxide slurry of preparation thus also has good mobility and stability when having high solids content.The above-mentioned nano oxide slurry that makes is made the satisfactory micron-size spherical powder of size-grade distribution by drying process with atomizing, and then heat-treat, can obtain nanostructure spherical oxide powder.
The mechanism of action that the present invention adopts surface-modifying agent to improve the nano oxide powder fluidity of slurry is:
The nano oxide powder specific surface area is large, and the surface exists a large amount of unsaturated link(age)s.In the dispersion system take water as disperse phase, nano oxide powder and water molecules interphase interaction form is combined water in a large number.In the nanometer oxide dispersion of high solid loading was, this water of constitution can make the mobility of nano oxide slurry descend.When adding acid reagent, the H of its ionization
+Can be in the nano oxide powder surface adsorption, and change the character on nano-oxide surface, thereby change between nano-oxide and water molecules medium, the interaction between nano oxide powder, make stronger repulsive force is arranged between nano oxide powder, reduce the content of water of constitution, thereby play the solid content of adjusting nano-oxide slurry and the effect of mobility.
Take nano zircite as example, because it has high-specific surface area, high surface energy and high Surface binding energy, and surface atom lacks adjacent atom, has nonsaturation, is easy to form one deck hydration shell in the aqueous solution, and nano zirconium oxide powder can adsorb H
+And OH
-And it is charged.And at iso-electric point (IEP), near pH=5, due to its absorption H
+With absorption OH
-And the positive potential that produces and negative potential equate, be that the nano oxide powder surface shows as neutral, magnetism between nano-oxide particles is greater than the repulsive force between electrostatic double layer, and particle easily occurs to reunite and coagulation, and namely the aggregation stability of nano-oxide suspension is the poorest at this moment; In the acid range away from iso-electric point in (pH=2～3) or alkaline range (pH=9～11), the nano zirconium oxide powder surface adsorption superfluous H
+Or OH
-Ion has increased the thickness of electrostatic double layer, makes the nano zircite particle surface have higher potential barrier, and intergranular electronic double layer repulsion power is larger, because the electrostatic repulsion effect of like charges disperses powder.Under the strong acid condition of pH＜1 or pH under 11 highly basic condition, because the too much introducing of salt increases the electrolyte concentration in solution, not only make with electrostatic double layer in fixed layer with the compressed electrostatic double layer that enters of electrical ion, and together with the gegenion also compressed electrostatic double layer that enters, thereby reduced the carried charge of particle surface, Zeta potential is reduced, the aggregation stability variation of system; And under the acidic conditions of pH＜5, the stability of nano zircite suspension obviously is better than the suspension stability under alkaline condition, and this can explain by the surface characteristic of Zirconium powder.Under alkaline condition, the zirconia particles surface is owing to having adsorbed OH
-Ion and electronegative, the OH on surface
-Combine with hydrogen bond with the water in solution, in this, hydrogen bond makes between Zirconia particles and is connected with each other, thereby easily reunites.By upper, the mobility of pH=3～4 o'clock nano zircite slurry and stability are best.
Beneficial effect of the present invention:
The nano oxide slurry that the method is produced also has good mobility when having high solids content, good stability is specially adapted to hot-spraying techniques and prepares nanostructured thermal barrier coatings and prepare nano-structural ceramic with the preparation of micron order nano-oxide spherical powder with micron order nano-oxide spherical powder or high-sintering process; Preparation technology is simple, easy and simple to handle, safe and reliable, and low cost of manufacture is suitable for suitability for industrialized production.
Description of drawings
Accompanying drawing 1 is the electron scanning micrograph of the yttrium stable zirconium oxide spherical powder of embodiment 1 preparation;
Accompanying drawing 2 is the electron scanning micrograph of the alumina powder of embodiment 3 preparations.
Embodiment
Below in conjunction with following specific embodiment, summary of the invention of the present invention is described further.
Embodiment 1:
1) dose volume is than the salpeter solution that is 5%: get concentrated nitric acid (15.7mol/L) 500mL, add pure water 9500mL, be configured to the 10.0L salpeter solution, stir;
2) taking particle diameter is that the yttrium stable zirconium oxide powder 10.0kg of 15nm is placed in the 50L container, adds deionized water 20.0kg, stirs and forms the dried shape thing of yttrium stable zirconium oxide;
3) salpeter solution with step 1) preparation slowly joins step 2) in the dried shape thing of yttrium stable zirconium oxide of preparation, the limit edged stirs, the yttrium stable zirconium oxide flow-like slurry that adjusting obtains pH to 3～4 (approximately needs salpeter solution 80～120mL), its solid load approximately 33%;
4) the yttrium stable zirconium oxide slurry of step 3) preparation is made by drying process with atomizing the micron-size spherical powder that granularity is distributed as 2 μ m～80 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the yttrium stable zirconium oxide micron-size spherical powder suction cyclonic separator of exhausting with drying;
5) with yttrium stable zirconium oxide micron-size spherical powder in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours: remove the residual water-content in powder, then through screening, obtain nanostructured Yt-stable spherical zircite powder for thermal spraying.The electron scanning micrograph of Yt-stable spherical zircite powder is seen accompanying drawing 1.
Embodiment 2:
1) dose volume is than the formic acid solution that is 20%: get 2.0L technical grade formic acid, add pure water 8.0L, be configured to the formic acid solution of 10.0L, stir;
2) taking particle diameter is that the yttrium stable zirconium oxide powder 10.0kg of 20nm is placed in the 50L container, adds the 6.50kg deionized water, forms the dried shape thing of yttrium stable zirconium oxide after stirring;
3) formic acid solution with step 1) preparation adds 2) the dried shape thing of yttrium stable zirconium oxide in, the limit edged stirs, dried shape thing is fluidify shape slurry slowly, regulates the yttrium stable zirconium oxide slurry that obtains pH to 3～4, its solid load approximately 60%;
4) the yttrium stable zirconium oxide slurry that step 3) is obtained makes by drying process with atomizing the micron-size spherical powder that granularity is distributed as 10 μ m～120 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the spherical powder suction cyclonic separator of exhausting with drying; This process spherical powder is still nanostructure;
5) screening: because spray-dired spherical powder has certain size-grade distribution (10 μ m～120 μ m), by screening, choose the powder of the product grading scope 20 μ m that meet Thermal Barrier Coating Layers Prepared By Plasma Spraying and use～120 μ m, other powder can be made colloid, mist projection granulating again more again;
6) thermal treatment: with the yttrium stable zirconium oxide powder of granularity 20 μ m～120 μ m in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours: remove the residual water-content in powder, decompose the organic reagent in powder, powder is through Overheating Treatment, particle diameter can diminish, through screening, obtain the nanostructured Yt-stable spherical zircite powder for thermal spraying of granularity 20 μ m～90 μ m again.
Embodiment 3:
1) hydrochloric acid soln preparation 10%(volume ratio): get concentrated hydrochloric acid 1000mL, add pure water 9000mL, be configured to the hydrochloric acid soln of 10.0L, stir;
2) taking particle diameter is that the alumina powder 10.0kg of 40nm is placed in the 50L container, adds deionized water 9.90kg, forms the dried shape thing of aluminum oxide after stirring;
3) hydrochloric acid soln with step 1) preparation adds step 2) in the dried shape thing of the aluminum oxide of preparation, the limit edged stirs, dried shape thing is fluidify shape slurry slowly, regulates the aluminum oxide slurry (approximately needing hydrochloric acid soln 100mL) obtain pH to 2～5, its solid load approximately 50%;
4) the aluminum oxide slurry of step 3) is made by drying process with atomizing the micron-size spherical powder that granularity is distributed as 5 μ m～120 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the spherical powder suction cyclonic separator of exhausting with drying;
5) screening: because spray-dired spherical powder has certain size-grade distribution (5 μ m～120 μ m), by screening, choose the powder (20 μ m～120 μ m) that meets the product grading scope that Thermal Barrier Coating Layers Prepared By Plasma Spraying uses, other powder can be made colloid, mist projection granulating again more again;
6) thermal treatment of powder: with the powder of granularity 20 μ m～120 μ m in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours; Remove the residual water-content in powder, powder is through Overheating Treatment, and particle diameter can diminish, then through screening, obtains thermospray or the sintered ceramic nanostructure ball-aluminium oxide powder of granularity 20 μ m～90 μ m.The electron scanning micrograph of powder is seen accompanying drawing 2.
Embodiment 4:
1) acetic acid solution preparation 40%(volume ratio): get technical grade acetic acid 4.0L, add pure water 6.0L, be configured to the acetic acid solution of 10.0L, stir;
2) taking particle diameter is that the alumina powder 10.0kg of 30nm is placed in the 50L container, adds the 19.90kg deionized water, forms the dried shape thing of aluminum oxide after stirring;
3) acetic acid solution with step 1) preparation adds 2) alumina dry shape thing in, the limit edged stirs, alumina dry shape thing slowly becomes aluminum oxide flow-like slurry, regulates the aluminum oxide fluid that obtains pH to 3～4, its solid load approximately 33%;
4) slurry is made by drying process with atomizing the micron-size spherical powder that granularity is distributed as 2 μ m～80 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the spherical powder suction cyclonic separator of exhausting with drying;
5) with powder in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours: remove the residual water-content in powder, decompose the organic reagent in powder, obtain thermospray or sintered ceramic with nanostructure ball-aluminium oxide powder.
Embodiment 5:
1) acetic acid solution preparation 20%(volume ratio): get technical grade acetic acid 2.0L, add pure water 8.0L, be configured to the acetic acid solution of 10.0L, stir;
2) taking particle diameter is that the SiO 2 powder 10.0kg of 10nm is placed in the 50L container, adds deionized water 9.90kg, forms the dried shape thing of silicon-dioxide after stirring;
3) acetic acid solution with step 1) preparation adds step 2) the dried shape thing of silicon-dioxide in, the limit edged stirs, the dried shape thing of silicon-dioxide slowly becomes silicon-dioxide flow-like slurry, regulates the silicon-dioxide fluid obtain pH to 2-5, its solid load approximately 50%;
4) slurry is made by drying process with atomizing the micron-size spherical powder that granularity is distributed as 10 μ m～120 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the spherical powder suction cyclonic separator of exhausting with drying;
5) thermal treatment of powder: with the powder of granularity 10 μ m～120 μ m in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours; Remove the residual water-content in powder, powder is through Overheating Treatment, and particle diameter can diminish, then through screening, obtains meeting the nanostructure preparing spherical SiO 2 powder of Thermal Barrier Coating Layers Prepared By Plasma Spraying granularity 20 μ m～90 μ m.
Embodiment 6:
1) salpeter solution preparation 5%(volume ratio): get concentrated nitric acid (15.7mol/L) 500mL, add pure water 9500mL, be configured to the salpeter solution of 10.0L, stir;
2) take the yttrium stable zirconium oxide powder 8.0kg that particle diameter is 10nm, the alumina powder 2.0kg that particle diameter is 30nm and be placed in the 50L container, add the 9.90kg deionized water, form dried shape thing after stirring;
3) salpeter solution with step 1) preparation adds step 2) dried shape thing in, the limit edged stirs, dried shape thing is fluidify shape slurry slowly, and regulating the yttrium stable zirconium oxide slurry obtain pH to 3～4 (approximately needs salpeter solution 80～120mL), its solid load approximately 50%;
4) slurry is made by drying process with atomizing the micron-size spherical powder that granularity is distributed as 20 μ m～120 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the spherical powder suction cyclonic separator of exhausting with drying;
5) screening: because spray-dired spherical powder has certain size-grade distribution (10 μ m～120 μ m), by screening, choose the powder (20 μ m～120 μ m) that meets the product grading scope that Thermal Barrier Coating Layers Prepared By Plasma Spraying uses, other powder can be made colloid, mist projection granulating again more again;
6) thermal treatment of powder: with the powder of granularity 20 μ m～120 μ m in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours; Remove the residual water-content in powder, powder is through Overheating Treatment, and particle diameter can diminish, then through screening, obtains yttrium stable zirconium oxide and the alumina composite powder of granularity 20 μ m～90 μ m.
Embodiment 7:
1) salpeter solution preparation 1%(volume ratio): get concentrated nitric acid (15.7mol/L) 100mL, add pure water 9900mL, be configured to the salpeter solution of 10.0L, stir;
2) take nanometer cobalt oxide that particle diameter is 60nm and the composite powder 10.0kg of nano-nickel oxide, be placed in the 50L container, add deionized water 6.50kg, form dried shape thing after stirring;
3) salpeter solution with preparation adds 2) in regulate pH to 3～4(and approximately need salpeter solution 80～120mL), the limit edged stirs, dried shape thing is fluidify shape slurry gradually, its solid load approximately 60%;
4) slurry is made by drying process with atomizing the micron-size spherical powder that granularity is distributed as 20 μ m～120 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the spherical powder suction cyclonic separator of exhausting with drying;
5) thermal treatment of powder: with the powder of granularity 20 μ m～120 μ m in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours; Remove the residual water-content in powder, obtain the nanometer cobalt oxide of granularity 20 μ m～120 μ m/nanometer nickel oxide composite powder end, be applied to thermospray or pyroceramic;
6) screening: because spray-dired spherical powder has certain size-grade distribution (20 μ m～120 μ m), can be by screening, choose the nanometer cobalt oxide that more meets the product grading scope that Thermal Barrier Coating Layers Prepared By Plasma Spraying uses/nanometer nickel oxide composite powder end (20 μ m～90 μ m).
Embodiment 8
1) dose volume is than the salpeter solution that is 5%: get concentrated nitric acid (15.7mol/L) 500mL, add pure water 9500mL, be configured to the 10.0L salpeter solution, stir;
2) salpeter solution with the step 1) preparation adds deionized water 20.0kg, stir, then join in the 10kg yttrium stable zirconium oxide, the limit edged stirs, the yttrium stable zirconium oxide flow-like slurry that adjusting obtains pH to 3～4 (approximately needs salpeter solution 80～120mL), its solid load approximately 33%;
3) with step 2) preparation the yttrium stable zirconium oxide slurry make by drying process with atomizing the micron-size spherical powder that granularity is distributed as 2 μ m～80 μ m, spray pattern is centrifugal or two streamings, spray-dired inlet temperature is 160 ℃～200 ℃, air outlet temperature is controlled at 80 ℃～120 ℃, and the height of temperature is regulated and is limited with the abundant drying of powder; Subsequently by collecting in the yttrium stable zirconium oxide micron-size spherical powder suction cyclonic separator of exhausting with drying;
4) with yttrium stable zirconium oxide micron-size spherical powder in 500 ℃～1000 ℃ thermal treatments of carrying out 1 hour～5 hours: remove the residual water-content in powder, then through screening, obtain nanostructured Yt-stable spherical zircite powder for thermal spraying.
Claims (1)
1. method for preparing nano oxide slurry is characterized in that: comprise the following steps:
1) solution of the acid surface-modifying agent of preparation;
2) preparation pH is the nano oxide slurry of 2-5, and described pH is that the nano oxide slurry of 2-5 is by a kind of the preparing in following two kinds of methods:
Method A: the acidic surface modifier solution that step 1) is prepared joins in the dried shape thing of nano oxide powder, the limit edged stirs, until formation pH is 2～5 nano oxide slurry, the dried shape thing of described nano oxide powder obtains by add the entry stirring in nano oxide powder;
Method B: the acidic surface modifier solution of acidic surface properties-correcting agent or step 1) preparation first is added to the water, stirs, then join in nano oxide powder, the limit edged stirs, until formation pH is 2～5 nano oxide slurry; In described method A or method B, the weight ratio of nano oxide powder and water is 2:8～7:3
Wherein, described step 2) nano-oxide in is one or more the mixing in yttrium stabilized nanoscale zirconium white, nano titanium oxide, nano aluminium oxide, nano silicon, nanometer cobalt oxide, nano-nickel oxide, and its particle diameter is 3～100nm;
Wherein: the acidic surface properties-correcting agent in described step 1) is one or more the mixing in formic acid, acetic acid, polyacrylic acid, hydrochloric acid, nitric acid.
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