阅读说明：本技术 一种水溶性氧化锆前驱体及其制备方法与应用 (Water-soluble zirconium oxide precursor and preparation method and application thereof ) 是由 邱文丰 曹艺 于 2020-11-19 设计创作，主要内容包括：本发明公开了一种水溶性氧化锆前驱体及其制备方法与应用。所述方法包括以下步骤：将醋酸锆加入到去离子水或醇类溶剂中,再缓慢加入乙酰丙酮进行反应,然后再缓慢滴加三乙胺进行缩聚反应,最后加入酸调节溶液pH值为4～6,再通过减压蒸馏或旋转蒸发除去溶剂,得到水溶性氧化锆前驱体。本发明的氧化锆陶瓷前驱体溶于水或有机溶剂得到氧化锆陶瓷前驱体溶液,且通过改变氧化锆前驱体在溶液中的固含量可调节前驱体溶液粘度,因此加工工艺性优良。该前驱体溶液还可用于制备氧化锆陶瓷粉体和氧化锆陶瓷空心微球。本发明克服了传统无机法制备的氧化锆前驱体工艺性差的缺点以及有机法制备的氧化锆前驱体不能溶于水,使用受限的缺点。(The invention discloses a water-soluble zirconium oxide precursor and a preparation method and application thereof. The method comprises the following steps: adding zirconium acetate into deionized water or an alcohol solvent, slowly adding acetylacetone for reaction, then slowly dropwise adding triethylamine for polycondensation reaction, finally adding an acid to adjust the pH value of the solution to 4-6, and removing the solvent through reduced pressure distillation or rotary evaporation to obtain the water-soluble zirconium oxide precursor. The zirconia ceramic precursor is dissolved in water or an organic solvent to obtain a zirconia ceramic precursor solution, and the viscosity of the precursor solution can be adjusted by changing the solid content of the zirconia precursor in the solution, so that the processing manufacturability is excellent. The precursor solution can also be used for preparing zirconia ceramic powder and zirconia ceramic hollow microspheres. The method overcomes the defects of poor manufacturability of the zirconia precursor prepared by the traditional inorganic method and the defects of water insolubility and limited use of the zirconia precursor prepared by the organic method.)

1. A preparation method of a water-soluble zirconia precursor is characterized by comprising the following steps:

adding zirconium acetate into a certain amount of deionized water or alcohol solvent, and heating for 20-30 minutes at 30-90 ℃; adding acetylacetone, and reacting at 30-90 ℃ for 30-60 minutes; then adding triethylamine, and carrying out polycondensation reaction for 2-6 hours at the temperature of 30-90 ℃; and cooling to 20-30 ℃, adding a certain amount of acid to adjust the pH value of the solution to 4-6, and removing the solvent to obtain the water-soluble zirconium oxide precursor.

2. The method for preparing the water-soluble zirconium oxide precursor according to claim 1, wherein the molar ratio of acetylacetone to zirconium acetate is 0.4 to 2: 1; the molar ratio of triethylamine to zirconium acetate is 1-4: 1.

3. the preparation method of the water-soluble zirconia precursor according to claim 1, wherein the acetylacetone is added dropwise within 30-60 minutes; and adding triethylamine in a dropwise manner, wherein the dropwise addition is completed within 1-2 hours.

4. The method for preparing the water-soluble zirconium oxide precursor according to claim 1, wherein the mass ratio of the zirconium acetate solution to the deionized water or the alcohol solvent is 1: 0.5 to 10.

5. The method for preparing a water-soluble zirconia precursor according to claim 1, wherein the alcoholic solvent is at least one of methanol, ethanol, n-propanol, isopropanol and ethylene glycol;

the acid is at least one of formic acid, acetic acid, propionic acid, oxalic acid, malic acid, citric acid, dilute sulfuric acid and dilute nitric acid, and the mass concentration of the dilute sulfuric acid and the dilute nitric acid is 3-5%.

6. The method for preparing the water-soluble zirconia precursor according to claim 1, wherein the solvent is removed by rotary evaporation or reduced pressure distillation, wherein the temperature of the rotary evaporation is 50-80 ℃, and the pressure is less than-0.05 Mpa; the temperature of the reduced pressure distillation is 60-90 ℃, and the pressure is below-0.05 Mpa.

7. A water-soluble zirconia precursor obtained by the method of any one of claims 1 to 6.

8. A water-soluble zirconia precursor solution, which is obtained by mutual dissolution of the water-soluble zirconia precursor of claim 7 and a solvent, wherein the solvent is at least one of water, methanol, ethanol, n-propanol, isopropanol, ethylene glycol monomethyl ether and ethylene glycol ethyl ether.

9. The water-soluble zirconia precursor solution according to claim 8, wherein the mass concentration of the water-soluble zirconia precursor solution is 30 to 70%.

10. Use of a water-soluble zirconia precursor according to claim 7 and a water-soluble zirconia precursor solution according to claim 8 or 9 for the preparation of zirconia ceramics and zirconia ceramic hollow microspheres.

Technical Field

The invention belongs to the field of zirconia precursors, and particularly relates to a water-soluble zirconia precursor, a solution thereof, a preparation method thereof and application of the precursor solution in preparation of zirconia and zirconia ceramic hollow microspheres.

Background

Zirconia ceramics is a multifunctional inorganic material with important application value, has good semiconductor characteristics, acid-base amphiprotic property and oxygen sensitivity, and is widely applied to catalyst carriers, catalysts, piezoelectric ceramics and optical materials. Meanwhile, the zirconium oxide has the characteristics of high hardness, high chemical stability, high temperature resistance, wear resistance, good biocompatibility and the like, and can be used as a structural material to be applied to the fields of cutting tools, ceramic mechanical materials, ceramic teeth, ceramic bones and the like.

At present, the synthesis methods of zirconia mainly include precipitation methods, microemulsion methods, sol-gel methods, hydrothermal (or solvothermal) methods, freeze drying methods, high-temperature spray pyrolysis methods, and the like. Although the freeze-drying method and the high-temperature spray pyrolysis method are simple to operate and have high yield, the method has the problems of low product purity, large particle size, difficulty in adjustment and the like. The micro-emulsion method for preparing the zirconium oxide can well control the size of particles of the zirconium oxide, but the subsequent emulsion breaking process is complicated, so that the application of the zirconium oxide is greatly limited. Whether an inorganic zirconium salt or an organic zirconium alkoxide precursor is used for the precipitation method, the sol-gel method, or the hydrothermal (or solvothermal) method, it has very high hydrolysis reaction activity, and thus causes severe agglomeration of zirconia particles, making it difficult to control the particle size. Therefore, in order to overcome a series of negative effects brought by high hydrolysis reaction activity of the traditional zirconia precursor, the synthesis of a novel water-soluble zirconia precursor for preparing zirconia ceramics becomes an effective means for solving the problems.

The zirconia ceramic hollow microsphere has a new material with a special hollow structure, has the characteristics of small density, excellent thermal stability, low heat conductivity coefficient and the like, can be used as a hollow filler and thermal insulation material, is uniformly dispersed in a matrix material, reduces the quality of the composite material, and improves the mechanical property and the thermal property of the composite material. Due to the difficulty of preparation, no available ceramic hollow microsphere product exists at present in China, and micron-sized ceramic hollow microsphere products of American companies are strictly forbidden to be transported in China. By referring to the preparation process and experience of resin-based hollow microspheres and by utilizing the excellent processing manufacturability of polymer ceramic precursors, the preparation technology of the ceramic hollow microspheres is developed by the technical means of spray drying which is easy for large-scale preparation, and the micron-sized (the particle size is less than 50 mu m) zirconia hollow microspheres with the temperature-resistant grade of more than 1000 ℃ are prepared. Because the technical route of spray drying in an air atmosphere is selected to prepare the required hollow microsphere material, the percentage of the target element required in the precursor solution and the selection of the solvent of the precursor solution are key problems to be solved. In order to solve the problems, required inorganic elements are introduced into a main chain of a polymer to increase the content of the inorganic elements and ensure that the polymer has higher polymerization degree; meanwhile, the synthesized polymer macromolecule is soluble in water, so that the content of organic solution in the precursor is reduced.

Therefore, it is necessary to develop a water-soluble zirconia precursor for preparing zirconia ceramics and zirconia ceramic hollow microspheres simply, safely and controllably.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a water-soluble zirconium oxide precursor.

The invention also aims to provide a water-soluble zirconia precursor prepared by the method.

The invention also aims to provide application of the water-soluble zirconia precursor in preparing zirconia ceramics and zirconia ceramic hollow microspheres.

The invention further aims to provide a water-soluble zirconium oxide precursor solution and application thereof. The water-soluble zirconia precursor in the water-soluble zirconia precursor solution is prepared by the method.

The purpose of the invention is realized by the following technical scheme:

a preparation method of a water-soluble zirconia precursor comprises the following steps:

adding zirconium acetate into a certain amount of deionized water or alcohol solvent, and heating for 20-30 minutes at 30-90 ℃; adding acetylacetone, and reacting at 30-90 ℃ for 30-60 minutes; then adding triethylamine, and carrying out polycondensation reaction for 2-6 hours at the temperature of 30-90 ℃; and cooling to 20-30 ℃, adding a certain amount of acid to adjust the pH value of the solution to 4-6, and removing the solvent to obtain the water-soluble zirconium oxide precursor.

In a preferred technical scheme, the mass ratio of the zirconium acetate to the deionized water or the alcohol solvent is 1: 0.5 to 10.

In a preferred technical scheme, the alcohol solvent is at least one of methanol, ethanol, n-propanol, isopropanol and ethylene glycol.

In the preferred technical scheme, the molar ratio of acetylacetone to zirconium acetate is 0.4-2: 1. the acetylacetone is added in a dropwise manner, the dropwise addition is controlled within 30-60 minutes, preferably 40 minutes, and the reaction is carried out under a reflux condition.

In the preferred technical scheme, the molar ratio of triethylamine to zirconium acetate is 1-4: 1. the triethylamine is added in a dropwise manner, the dropwise addition is controlled within 1-2 hours, preferably 1.5 hours, and the reaction is carried out under the condition of reflux. The concentration, the dripping time and the reaction temperature of triethylamine in the reaction system have great influence on the intensity of the polycondensation reaction, and finally the structure and the performance of the zirconia precursor are influenced. Under the technical conditions of the invention, the polycondensation reaction is mild and controllable, and the finally obtained zirconia precursor is uniform and stable, can be uniformly dispersed in water to form a long-term stable precursor solution, and can also be used for processing other zirconia ceramic materials.

In the preferable technical scheme, the acid is at least one of formic acid, acetic acid, propionic acid, oxalic acid, malic acid, citric acid, dilute sulfuric acid and dilute nitric acid, the mass concentration of the dilute sulfuric acid and the dilute nitric acid is 3-5%, other acids are chemically pure, and the stability of the zirconia precursor can be improved after the acid is added.

In the preferred technical scheme, the solvent is removed by adopting a rotary evaporation or reduced pressure distillation mode, wherein the temperature of the rotary evaporation is 50-80 ℃, and the pressure is below-0.05 Mpa; the temperature of the reduced pressure distillation is 60-90 ℃, and the pressure is below-0.05 Mpa; under the condition, the stability of the precursor can be effectively maintained while the solvent is effectively removed.

A water-soluble zirconia precursor prepared by the method. The zirconia precursor contains a-Zr-O-Zr-main chain structure.

The water-soluble zirconia precursor is applied to preparation of zirconia ceramics and zirconia ceramic hollow microspheres.

A water-soluble zirconia precursor solution is obtained by mutually dissolving the water-soluble zirconia precursor and a solvent, wherein the solvent is at least one of water, methanol, ethanol, n-propanol, isopropanol, ethylene glycol monomethyl ether and ethylene glycol ethyl ether.

In the preferred technical scheme, the mass concentration of the water-soluble zirconium oxide precursor solution is 30-70%.

The zirconia precursor solution prepared in the prior art has two types, namely a water phase solution and an organic phase solution, the water phase zirconia precursor solution is mostly an inorganic salt system and has no viscosity, and the zirconia precursor solution with the characteristics of a polymer solution is an organic phase solution and cannot be mixed with water, so that the application range is limited. The water-soluble zirconia solution prepared by the invention realizes the purpose of dissolving the polymer zirconia precursor in water, and the viscosity of the solution is controllable within 10-6000 mPa.s by adjusting the solid content of the zirconia precursor solution before the solution is prepared, and the solution has good processing property, and can be used for preparing zirconia blocks, composites, fibers, films, coatings, flat plates and other materials.

The water-soluble zirconia precursor solution is applied to preparation of zirconia ceramics and zirconia ceramic hollow microspheres.

Compared with the prior art, the invention has the following advantages and beneficial effects:

1. the raw materials adopted by the invention have wide sources, low price, mild preparation conditions, high material utilization rate and low energy consumption, and can greatly reduce the industrial production cost.

2. The water-soluble zirconium oxide precursor developed by the invention can be uniformly dissolved in water to form a stable solution, the retention period can be up to several months, the solid content and the viscosity can be adjusted, and the processability is excellent.

3. The zirconium oxide precursor developed by the invention can be dissolved in water, can be mutually dissolved with various organic solvents, and has wider application range.

4. The zirconia precursor aqueous solution developed by the invention is suitable for preparing zirconia ceramic hollow microspheres by a spray drying method, is simple to operate and is beneficial to large-scale industrial production.

Drawings

Fig. 1 is a diagram showing a zirconium oxide precursor prepared in example one dissolved in water.

Fig. 2 is a diagram showing a zirconium oxide precursor prepared in example two dissolved in water.

Fig. 3 is a diagram showing a zirconium oxide precursor prepared in example three dissolved in water.

Fig. 4 is a diagram showing a zirconium oxide precursor prepared in example four dissolved in water.

Fig. 5 is an infrared characteristic spectrum of the zirconia precursor prepared in example four.

FIG. 6 is a DSC of an aqueous solution of a zirconia precursor prepared in example IV.

FIG. 7 is a graph showing the thermal weight loss of the aqueous solution of the zirconia precursor prepared in example four.

Fig. 8 is a diagram showing a zirconium oxide precursor prepared in example v dissolved in ethanol.

FIG. 9 is an XRD pattern of a zirconia ceramic prepared at 1000 ℃ for example six.

FIG. 10 is a graph showing the thermogravimetric plot of the precursor of the hollow microspheres of zirconia ceramic in example VII.

FIG. 11 is an XRD pattern of the hollow microspheres of zirconia ceramic of example VII.

FIG. 12 is an SEM image of hollow zirconia ceramic microspheres of example VII.

FIG. 13 is a graph showing the thermogravimetric plot of the precursor of the hollow microspheres of zirconia ceramic in example eight.

FIG. 14 is an XRD pattern of the hollow microspheres of zirconia ceramic of example eight.

FIG. 15 is an SEM image of hollow zirconia ceramic microspheres of example eight.

FIG. 16 is an SEM image of hollow zirconia ceramic microspheres of example nine.

FIG. 17 is an SEM image of zirconia ceramic hollow microspheres of example ten.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.

Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.

Example one

Preparing a zirconium oxide precursor: 327g (1mol) of zirconium acetate was added to 1000g of deionized water and heated at 60 ℃ for 30 minutes; slowly adding 60g (0.6mol) of acetylacetone, controlling the dropping speed, completing within 30 minutes, and carrying out reflux reaction for 40 minutes at 60 ℃; then, 151.5g (1.5mol) of triethylamine is slowly added dropwise to carry out polycondensation reaction, the dropwise adding speed is controlled to be completed within 1 hour, and the reflux reaction is carried out for 3 hours at the temperature of 60 ℃; after cooling to 30 ℃, 9g (0.1mol) of oxalic acid is added to adjust the pH value of the solution to 5, and then the solvent is removed by rotary evaporation at 60 ℃ to obtain the water-soluble zirconium oxide Precursor (PNZ).

Preparing a zirconium oxide precursor solution: a precursor solution with the mass fraction of 30% is prepared by using the prepared PNZ and deionized water, the viscosity of the precursor solution is 400mPa & s, and a photo of the precursor solution stored for 3 months is shown as an attached figure 1.

Example two

Preparing a zirconium oxide precursor: 327g (1mol) of zirconium acetate was added to 1500g of deionized water and heated at 80 ℃ for 30 minutes; then 120g (1.2mol) of acetylacetone is slowly added, the dropping speed is controlled to be completed within 40 minutes, and the reflux reaction is carried out for 40 minutes at 80 ℃; then slowly dropwise adding 222.2g (2.2mol) of triethylamine for polycondensation reaction, controlling the dropwise adding speed to be completed within 1.5 hours, and carrying out reflux reaction for 3 hours at 80 ℃; after cooling to 30 ℃, 19.2g (0.1mol) of citric acid is added to adjust the pH value of the solution to 5, and then the solvent is removed by rotary evaporation at 60 ℃ to obtain the water-soluble zirconium oxide Precursor (PNZ).

Preparing a zirconium oxide precursor solution: a precursor solution with the mass fraction of 50% is prepared by using the prepared PNZ and deionized water, the viscosity of the precursor solution is 1300mPa & s, and a photo of the precursor solution stored for 3 months is shown as an attached figure 2.

EXAMPLE III

Preparing a zirconium oxide precursor: 327g (1mol) of zirconium acetate solution was added to 3000g of deionized water and heated at 70 ℃ for 40 minutes; slowly adding 180g (1.8mol) of acetylacetone, controlling the dropping speed, completing the reaction within 60 minutes, and carrying out reflux reaction at 70 ℃ for 40 minutes; then, 252.5g (2.5mol) of triethylamine is slowly added dropwise to carry out polycondensation reaction, the dropwise adding speed is controlled to be completed within 2 hours, and the reflux reaction is carried out for 4 hours at 70 ℃; after cooling to 30 ℃, 7.4g (0.1mol) of propionic acid is added to adjust the pH value of the solution to 5, and the solvent is removed by rotary evaporation at 70 ℃ to obtain the water-soluble zirconium oxide Precursor (PNZ).

Preparing a zirconium oxide precursor solution: a precursor solution with the mass fraction of 60% is prepared by using the prepared PNZ and deionized water, the viscosity of the precursor solution is 1900mPa & s, and a photo of the precursor solution stored for 3 months is shown in an attached figure 3.

Example four

Preparing a zirconium oxide precursor: 327g (1mol) of zirconium acetate solution was added to 3000g of deionized water and heated at 60 ℃ for 30 minutes; then 120g (1.2mol) of acetylacetone is slowly added, the dropping speed is controlled to be completed within 40 minutes, and the reflux reaction is carried out for 60 minutes at 60 ℃; then, 303g (3mol) of triethylamine is slowly added dropwise to carry out polycondensation reaction, the dropwise adding speed is controlled to be completed within 2 hours, and the reflux reaction is carried out for 4 hours at the temperature of 60 ℃; after cooling to 30 ℃, 6g (0.1mol) of acetic acid is added to adjust the pH value of the solution to 5, and then the solvent is removed by rotary evaporation at 60 ℃ to obtain the water-soluble zirconia Precursor (PNZ).

Preparing a zirconium oxide precursor solution: a precursor solution with the mass fraction of 70% is prepared by using the prepared PNZ and deionized water, the viscosity of the precursor solution is 2400mPa · s, and a photo of the precursor solution stored for 3 months is shown in an attached figure 4.

The PNZ polymer solid prepared in the way is characterized by infrared, and the infrared absorption peak of the characteristic group is shown in figure 5. The infrared absorption peak is positioned at 3419cm^-1O-H stretching vibration peak belonging to ligand; positioned at 1569cm^-1The absorption peak of (a) belongs to the C ═ O stretching vibration peak of the ligand; at 1450cm^-1Absorption peaks of (A) areC ═ C stretching vibration peak of ligand; is located at 1025cm^-1The absorption peak of (A) belongs to the C-CH of the ligand₃A stretching vibration peak.

A differential scanning thermal scan experiment was carried out on the PNZ 70% solids aqueous solution prepared above, and the DSC curve is shown in FIG. 6. The sample is heated to 600 ℃ in the air at a heating rate of 10 ℃/min, the endothermic peak at about 100 ℃ is mainly caused by the volatilization of the solvent of the PNZ precursor solution, the endothermic peak at about 203 ℃ is mainly caused by the melting of the PNZ precursor, the exothermic peak at about 360 ℃ is mainly caused by the decomposition and the heat release of the PNZ, and the exothermic peak at about 486 ℃ is mainly caused by the heat release of the zirconium oxide crystal.

The aqueous solution of PNZ with 70% solid content prepared above was subjected to a thermogravimetric test, and the thermogravimetric curve thereof is shown in FIG. 7. The sample is heated to 1000 ℃ in the air at a heating rate of 10 ℃ to have about the ceramic residual weight and finally obtain white solid powder, wherein the weight loss of about 100 ℃ is mainly caused by the loss of solvent water, and the weight loss of about 360 ℃ is mainly caused by the leaving of organic groups.

EXAMPLE five

Preparing a zirconium oxide precursor: 327g (1mol) of zirconium acetate solution was added to 3000g of ethanol and heated at 60 ℃ for 30 minutes; then 120g (1.2mol) of acetylacetone is slowly added, the dropping speed is controlled to be completed within 30 minutes, and the reflux reaction is carried out for 30 minutes at 60 ℃; then, 202g (2mol) of triethylamine is slowly added dropwise to carry out polycondensation reaction, the dropwise adding speed is controlled to be completed within 1 hour, and the reflux reaction is carried out for 2 hours at the temperature of 60 ℃; after cooling to 30 ℃, 4.6g (0.1mol) of formic acid is added to adjust the pH value of the solution to 5, and then the solvent is removed by rotary evaporation at 50 ℃ to obtain the water-soluble zirconia Precursor (PNZ).

Preparing a zirconium oxide precursor solution: a precursor solution with the mass fraction of 40% is prepared by using the prepared PNZ and ethanol solution, the viscosity of the precursor solution is 980 mPas, and a photo of the precursor solution stored for 3 months is shown in an attached figure 8.

EXAMPLE six

Preparation of zirconia powder: the PNZ polymer solid in the fourth example is put into an alumina crucible, sintered to 1000 ℃ in air atmosphere, and subjected to X-ray diffraction test, the XRD spectrum of the sample is shown as figure 9, and the peaks in the XRD spectrum are all characteristic peaks of zirconia.

EXAMPLE seven

The preparation method of the zirconia ceramic hollow microsphere comprises the following specific steps:

(a) 0.6g of cetyltrimethylammonium bromide, 0.1g of carboxymethylcellulose and 1g of polyethylene glycol 1000 were added to 100g of the zirconia precursor solution of example one (the solution obtained by adjusting the pH of the solution to 5 of example one), and the mixture was stirred uniformly to obtain a spray-dried solution, which was denoted as solution 1.

(b) And (b) enabling the solution 1 in the step (a) to enter a two-fluid atomization nozzle at a liquid inlet speed of 5mL/min, simultaneously introducing compressed air into the two-fluid nozzle at a flow speed of 20L/min, atomizing the precursor solution into fog drops under the combined action of the atomization nozzle and the compressed air, and instantly finishing the processes of solvent evaporation, particle forming and drying under the action of high temperature of 140 ℃ of the fog drops in a drying tower. And finally, depositing a sample into a sample collector with the aid of an exhaust device to obtain white powder which is a precursor of the zirconia ceramic hollow microsphere.

(c) And (c) putting the precursor of the hollow zirconia ceramic microspheres obtained in the step (b) into an alumina crucible, and roasting for 3 hours at 600 ℃ in an air atmosphere to obtain the hollow zirconia ceramic microspheres.

Performing a thermal weight loss test on the zirconia ceramic hollow microsphere precursor in the step (b), wherein the attached figure 10 is a thermal weight loss curve thereof. The sample was heated in air to 600 ℃ at a ramp rate of 10 ℃/min, the ceramming residual weight was about 63.96% and a white solid powder was finally obtained. In the figure, the weight loss at about 200 ℃ is mainly caused by the loss of the organic additive, and the weight loss at about 360 ℃ is mainly caused by the leaving of the organic group of the PNZ polymer precursor in the first embodiment.

And (c) carrying out X-ray diffraction test and scanning electron microscope test on the ceramic hollow microsphere sample in the step (c). FIG. 11 is an XRD spectrum of a hollow microsphere sample, and peaks in the XRD spectrum are all characteristic peaks of zirconium oxide. FIG. 12 is an SEM image of a sample of hollow microspheres, where the sample has high integrity and narrow particle size distribution.

Example eight

The preparation method of the zirconia ceramic hollow microsphere comprises the following specific steps:

(a) 1.2g of cetyltrimethylammonium bromide, 0.2g of hydroxymethyl cellulose and 3g of polyethylene glycol 600 were added to 100g of the zirconium oxide precursor solution of example four (the solution obtained by adjusting the solution to a pH value of 5 in example four), and the mixture was stirred uniformly to obtain a spray-dried solution, which was denoted as solution 1.

(b) And (b) enabling the solution 1 in the step (a) to enter a two-fluid atomization nozzle at a liquid inlet speed of 5mL/min, simultaneously introducing compressed air into the two-fluid nozzle at a flow speed of 20L/min, atomizing the precursor solution into fog drops under the combined action of the atomization nozzle and the compressed air, and instantly finishing the processes of solvent evaporation, particle forming and drying under the action of high temperature of 140 ℃ of the fog drops in a drying tower. And finally, depositing a sample into a sample collector with the aid of an exhaust device to obtain white powder which is a precursor of the zirconia ceramic hollow microsphere.

(c) And (c) putting the precursor of the hollow zirconia ceramic microspheres obtained in the step (b) into an alumina crucible, and roasting for 1 hour at 1000 ℃ in an air atmosphere to obtain the hollow zirconia ceramic microspheres.

Performing a thermal weight loss test on the zirconia ceramic hollow microsphere precursor in the step (b), wherein the attached figure 13 is a thermal weight loss curve thereof. The sample was heated in air at a ramp rate of 10 ℃/min to 1000 ℃ with a ceramization residue weight of about 62.12% and a white solid powder was finally obtained. In the figure, the weight loss at about 200 ℃ is mainly caused by the loss of the organic additive, and the weight loss at about 360 ℃ is mainly caused by the leaving of the organic group of the PNZ polymer precursor in the fourth embodiment.

And (c) carrying out X-ray diffraction test and scanning electron microscope test on the ceramic hollow microsphere sample in the step (c). FIG. 14 is an XRD spectrum of a hollow microsphere sample, and peaks in the XRD spectrum are all characteristic peaks of zirconium oxide. FIG. 15 is an SEM image of a sample of hollow microspheres showing high sample integrity and narrow particle size distribution.

Example nine

The preparation method of the zirconia ceramic hollow microsphere comprises the following specific steps:

(a) 0.6g of sodium dodecyl benzene sulfonate, 0.2g of hydroxymethyl cellulose and 1g of polyethylene glycol 1000 are added into 100g of the zirconium oxide precursor solution in the first embodiment (the solution obtained by adjusting the pH value of the solution to 5 in the first embodiment), and the mixture is uniformly stirred to obtain a spray-dried solution, which is marked as solution 1.

(b) And (b) feeding the solution 1 in the step (a) into a two-fluid atomizing nozzle at a liquid inlet speed of 20mL/min, simultaneously introducing compressed air into the two-fluid nozzle at a flow speed of 40L/min, atomizing the precursor solution into fog drops under the combined action of the atomizing nozzle and the compressed air, and instantly finishing the processes of solvent evaporation, particle forming and drying under the action of high temperature of 200 ℃ of the fog drops in a drying tower. And finally, depositing a sample into a sample collector with the aid of an exhaust device to obtain white powder which is a precursor of the zirconia ceramic hollow microsphere.

(c) And (c) putting the precursor of the hollow zirconia ceramic microspheres obtained in the step (b) into an alumina crucible, and roasting for 2 hours at 800 ℃ in an air atmosphere to obtain the hollow zirconia ceramic microspheres.

And (c) carrying out scanning electron microscope test on the ceramic hollow microsphere sample in the step (c). FIG. 16 is an SEM image of a sample of hollow microspheres, where the sample has high integrity and narrow particle size distribution.

Example ten

The preparation method of the zirconia ceramic hollow microsphere comprises the following specific steps:

(a) 0.8g of sodium dodecylbenzenesulfonate, 0.1g of carboxymethylcellulose and 1g of polyethylene glycol 2000 were added to 100g of the zirconia precursor solution of example v (the solution obtained by adjusting the pH of the solution to 5 of example v), and the mixture was stirred uniformly to obtain a spray-dried solution, which was denoted as solution 1.

(b) And (b) feeding the solution 1 in the step (a) into a two-fluid atomizing nozzle at a liquid inlet speed of 5mL/min, simultaneously introducing compressed air into the two-fluid nozzle at a flow speed of 20L/min, atomizing the precursor solution into fog drops under the combined action of the atomizing nozzle and the compressed air, and instantly finishing the processes of solvent evaporation, particle forming and drying under the action of high temperature of 180 ℃ of the fog drops in a drying tower. And finally, depositing a sample into a sample collector with the aid of an exhaust device to obtain white powder which is a precursor of the zirconia ceramic hollow microsphere.

(c) And (c) putting the precursor of the hollow zirconia ceramic microspheres obtained in the step (b) into an alumina crucible, and roasting for 2 hours at 800 ℃ in an air atmosphere to obtain the hollow zirconia ceramic microspheres.

And (c) carrying out scanning electron microscope test on the ceramic hollow microsphere sample in the step (c). FIG. 17 is an SEM image of a sample of hollow microspheres showing high sample integrity and narrow particle size distribution.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.