Liquid forming method for preparing ceramic microspheres through alkoxide hydrolysis method

Abstract

The invention discloses a liquid forming method for preparing ceramic microspheres by an alkoxide hydrolysis method, which comprises the following steps: preparing an initial phase solution, a water phase, an oil phase and an extraction solution, taking the center of a coaxial needle tube as the initial phase solution, the secondary outer layer as the water phase and the outermost layer as the oil phase, and controlling the flow velocity ratio of the initial phase solution to the water phase and the flow velocity ratio of the initial phase solution to the oil phase; the emulsion liquid drops dispersed in the oil phase solution in the outflow tube of the coaxial needle tube are continuous spherical emulsion liquid drops, and the outflow tube is placed in a water bath environment; the liquid drops flowing out of the pipe are solidified in an extraction solution in a water bath state, and an extraction solution containing microspheres is obtained; carrying out vacuum fractionation on the extract liquor to recover an oil phase, and carrying out vacuum drying to obtain a microsphere blank; and firing the microsphere blank according to the firing temperature of the metal oxide of the metal alkoxide to obtain a finished product. According to the invention, fine oxide crystal grains with high activity are grown in situ through alcoholate hydrolysis, a surfactant is added to control the fine oxide crystal grains to form balls in an oil phase, and the ceramic microspheres with high roundness and uniform particle size are obtained through multi-stage water bath curing and sintering.

Description

Technical Field

[0001] The invention relates to the field of ceramic microspheres, and in particular to a liquid forming method for preparing ceramic microspheres by an alkoxide hydrolysis method. Background Art

[0002] Common preparation methods for ceramic microspheres include emulsification, sol-gel, and spray drying. Emulsification and sol-gel generally use the drop ball method to suspend and plasticize in the medium to form spheres, or use electrophoresis to make the particles directional agglomerate into spheres. Patent CN102166504.A reports a device and method for preparing gel microspheres by electrostatic drop ball method, adding a configured precursor emulsion to the electrostatic device, adding a centrifuge and a rotating cup to the electrostatic droplet generating device, optimizing the electric field distribution to change the dispersion of the droplets and improve the contact and inclusion effect of the solidifying liquid on the precursor emulsion. Patent CN110154201.A reports a method and device for preparing ceramic microspheres by suspension photocuring, and the formation of spherical droplets depends on the sedimentation and transformation of the droplets in the configured viscous suspending agent.

[0003] The disadvantage of the drop ball method is that it is difficult to ensure that the precursor is uniformly and stably suspended in the medium in the form of a sphere to complete the solidification, and during the solidification process, multiple droplets will not stick together. Improper handling during the process will result in spherical particles of different sizes or even strange shapes that are not spherical. In addition, when the drop ball method is used to form a ball, the amount of liquid droplets that form a ball is too large due to the resistance of surface tension to gravity, and the size of the formed microspheres is difficult to control. The process of droplets settling in the viscous suspension to transform into balls requires a certain amount of sedimentation time. During the process, the droplets are easily miscible with each other, and the shape of the blank is difficult to guarantee during solidification. Summary of the invention

[0004] The purpose of the invention is to provide a liquid forming method for preparing ceramic microspheres by an alkoxide hydrolysis method.

[0005] The innovation of the present invention lies in that the present invention in-situ grows highly active fine oxide grains through the hydrolysis of alcohol salts, uses a mobile oil phase as a shear phase to cut off the product in the outer layer while the reaction is in progress, adds a surfactant to control the product to form microsphere emulsion droplets with good sphericity in the mobile oil phase, controls the amount of cutting off by the flow rate difference between the oil phase and the product to achieve control of the size of the microspheres, realizes multi-stage water bath curing in an oil phase shear phase flow system-extraction solution dispersion system, effectively avoids the deformation of the product caused by the adhesion of the emulsion droplets in the curing process, and finally sinters to obtain ceramic microspheres with high roundness and uniform particle size.

[0006] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is:

[0007] A liquid forming method for preparing ceramic microspheres by an alkoxide hydrolysis method, characterized in that it comprises the following steps:

[0008] (1) preparing an initial phase solution: taking raw materials including the following mass fractions: 92-95% of liquid metal alkoxide, 2-5% of tetraethyl orthosilicate, and 1-3% of glass phase, and blending and dispersing them to obtain an initial phase solution;

[0009] (2) preparing an aqueous phase: adding polyvinyl alcohol and hexamethylenetetramine to water, stirring evenly, then adding a surfactant, adding an inorganic acid to adjust the pH to 2, stirring evenly to obtain an aqueous phase, wherein the amount of polyvinyl alcohol added is 2-3% of the mass of water, the amount of hexamethylenetetramine added is 2-3% of the mass of water, and the amount of the surfactant added is 0.3-0.5% of the mass of water;

[0010] (3) preparing the oil phase: taking the following raw materials by mass fraction: 75-85% of an organic long carbon chain alcohol, 10-20% of TOA, and 3-5% of Span 85, and mixing them uniformly to obtain an oil phase;

[0011] (4) preparing an extraction solution: taking raw materials including the following mass fractions: 75-85% of an organic short-chain alcohol, 10-20% of TOA, and 3-5% of Span 85, and mixing them uniformly to obtain an extraction solution;

[0012] (5) loading the initial phase solution, the water phase, and the oil phase into a coaxial needle tube, wherein the center of the coaxial needle tube is the initial phase solution, the second outer layer is the water phase, and the outermost layer is the oil phase, and the flow rate ratios of the initial phase solution to the water phase, and the initial phase solution to the oil phase are controlled so that the emulsion droplets dispersed in the oil phase solution at the outlet of the coaxial needle tube are continuous spherical emulsion droplets, and the outlet tube is placed in a water bath environment at 80 to 95° C.;

[0013] (6) dropping the liquid out of the tube into the extraction solution for extraction and solidification to obtain an extract containing microspheres, and placing the extract in a water bath at 75 to 90° C.;

[0014] (7) Recovering the oil phase from the extract containing the microspheres by vacuum distillation, and obtaining microsphere blanks by vacuum drying; and calcining the microsphere blanks at the calcination temperature of the metal oxide of the metal alkoxide to obtain the finished product.

[0015] Furthermore, the chemical formula of the liquid metal alkoxide is M m (OC x H y ) n , M is a metal element, the value of x is <5, and the liquid metal alkoxide is a combination of one or more liquid metal alkoxides.

[0016] Furthermore, the glass phase is an oxide or carbonate of calcium, magnesium or barium, and the powder fineness of the glass phase is D98<1.1 μm.

[0017] Furthermore, the hydrophile-lipophile balance (HLB) value of the surfactant in step (2) is in the range of 3 to 8.

[0018] Furthermore, the surfactant in step (2) is glyceryl monostearate or propylene glycol fatty acid ester.

[0019] Furthermore, the longest carbon chain of the organic long-chain alcohol in step (3) is greater than 9, and the longest carbon chain of the organic short-chain alcohol in step (4) is less than 5.

[0020] Furthermore, the flow rate ratio of the initial phase solution to the water phase is 0.5-1, the flow rate ratio of the initial phase solution to the oil phase is 0.1-0.7, the flow rate of the oil phase is greater than the flow rate of the water phase, and the flow rate of the initial phase solution is not greater than 0.5 mL / min.

[0021] The beneficial effects of the present invention are:

[0022] 1. In the present invention, metal alkoxide is used as the source of metal oxide in the ceramic, and the in-situ grown oxide crystal grains are finer and the particle surface activity is better.

[0023] 2. The present invention utilizes the pipeline design of the coaxial needle tube to achieve the meeting of multiple liquids at the same time, and to achieve the initiation of the alcoholysis reaction under the condition of flow rate difference.

[0024] 3. In the present invention, a surfactant is added to control the surface state of the powder generated during the alcoholysis reaction, and functional groups are grafted on the surface of particles with high surface oxygen atom activity to make them have certain lipophilic properties. The surfactant is selected to have an HLB value of about 3-8, which can ensure that the surfactant is slightly dispersed in water, and can form an oil-in-water stable emulsion after meeting oil, ensuring that the spherical shape of the emulsion remains stable during the movement of the outflow pipe.

[0025] 4. In the present invention, the huge flow rate difference between the initial phase solution and the water phase relative to the oil phase can achieve the cutoff of the initial phase solution / water phase. The initial phase solution / water phase with a slow flow rate serves as the dispersed phase, and the liquid with a fast flow rate serves as the continuous phase, and finally forms continuous spherical emulsion droplets dispersed in the oil phase. In this process, the size of the emulsion droplets can be controlled by the diameter of the outflow pipe and the flow rate, and finally form droplets of the target size.

[0026] 5. In the present invention, the solidification of continuous spherical emulsion droplets dispersed in the oil phase is achieved by a water bath in the outflow pipe. The solidification condition can be controlled and adjusted by extending the movement time in the water bath outflow pipe (i.e. extending the length of the outflow pipe in the water bath) to ensure that the droplets are pre-solidified into ceramic micro-greens when leaving the outflow pipe, thereby avoiding the deformation of the droplets when leaving the dropper in the conventional ball dropping method, and the deformation and uneven size of the green body caused by the adhesion of droplets in the medium.

[0027] 6. The present invention completely solidifies the previously pre-cured ball blank in a water bath in an extraction solution, and simultaneously utilizes a short-chain alcohol in the extraction solution to dissolve a portion of the water in the solidified blank, so that the ball blank skeleton structure of the microsphere can be better protected in the subsequent vacuum fractionation and oil phase filtration and vacuum drying process.

[0028] 7. The present invention generates metal oxide crystals in situ by alcohol salt hydrolysis method, and based on the hydrophilic and hydrophobic characteristics of oxide powder, adds surfactant for modification. The modified particles are irreversibly adsorbed at the interface of two immiscible liquids due to their partial wetting characteristics, reducing the surface energy of the oil-water interface, improving the anti-deformation ability of the oil-water interface, and realizing the spherical stabilization of the emulsion droplets. At the same time, the microsphere blanks are prepared by water bath curing during the continuous oil-driven flow of the microspheres in the pipeline, avoiding the problems of adhesion or deformation of the microsphere droplets during the curing process in the conventional drop ball method. Ceramic microspheres with controllable particle size and uniform overall distribution are produced by adjusting the flow rate and flow velocity difference and selecting the pipe diameter. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the finished product of Example 1.

[0030] Figure 2 This is a schematic diagram of the finished product of Example 2.

[0031] Figure 3 This is a schematic diagram of the finished product of Example 3.

[0032] Figure 4 Schematic diagram of the bonded ball blank made by conventional method. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Embodiment 1: A liquid forming method for preparing ceramic microspheres by an alkoxide hydrolysis method, comprising the following steps:

[0034] (1) Preparing an initial phase solution: Take the following raw materials by mass: 92% of liquid metal alkoxide, 5% of tetraethyl orthosilicate, and 3% of glass phase, and mix and disperse them to obtain an initial phase solution; the liquid metal alkoxide is tetraethyl titanate; the glass phase is calcium oxide, and the powder fineness of the glass phase is

[0035] D98<1.1μm.

[0036] (2) preparing the aqueous phase: adding polyvinyl alcohol and hexamethylenetetramine to water, stirring evenly, then adding a surfactant, adding an inorganic acid to adjust the pH to 2, stirring evenly to obtain an aqueous phase, wherein the amount of polyvinyl alcohol added is 2% of the mass of water, the amount of hexamethylenetetramine added is 2% of the mass of water, and the amount of surfactant added is 0.3% of the mass of water; the surfactant is glyceryl monostearate.

[0037] (3) preparing an oil phase: taking the following raw materials by mass fraction: 75% of an organic long-chain alcohol, 20% of octylamine (TOA), and 5% of Span 85, and mixing them evenly to obtain an oil phase; the organic long-chain alcohol is n-nonane;

[0038] (4) preparing an extraction solution: taking raw materials including the following mass fractions: 75% of an organic short-chain alcohol, 20% of octylamine (TOA), and 5% of Span 85, and mixing them evenly to obtain an extraction solution; the organic short-chain alcohol is n-butane;

[0039] (5) The initial phase solution, the water phase, and the oil phase are loaded into a coaxial needle tube, the center of the coaxial needle tube is the initial phase solution, the second outer layer is the water phase, and the outermost layer is the oil phase, so that the three solutions meet at the same point in layers, and the flow rate ratio of the initial phase solution to the water phase, and the initial phase solution to the oil phase is controlled. The flow rate ratio of the initial phase solution to the water phase is 0.5, and the flow rate ratio of the initial phase solution to the oil phase is 0.1. The flow rate of the oil phase is greater than the flow rate of the water phase. The flow rate of the initial phase solution is 0.2 mL / min, so that the emulsion droplets dispersed in the oil phase solution at the outlet of the coaxial needle tube are continuous spherical emulsion droplets, and the outlet tube is placed in a water bath environment at 80° C.;

[0040] (6) dropping the liquid out of the tube into the extraction solution for extraction and solidification to obtain an extract containing microspheres, and placing the extract in a water bath at 75° C.;

[0041] (7) The extract containing microspheres is subjected to reduced pressure fractionation to recover the oil phase, and vacuum drying is performed to obtain microsphere blanks; the microsphere blanks are fired at the firing temperature of the metal oxide of the metal alkoxide to obtain the finished product; the particle size of the microspheres is 90-110 μm, and the sphericity is 94%.

[0042] Example 2: A liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis, comprising the following steps:

[0043] (1) Preparing an initial phase solution: taking the following raw materials by mass fraction: 95% of liquid metal alkoxide, 2% of tetraethyl orthosilicate, and 3% of glass phase, and blending and dispersing them to obtain an initial phase solution; the liquid metal alkoxide is aluminum sec-butoxide; the glass phase is magnesium oxide, and the powder fineness of the glass phase is D98 <1.1 μm.

[0044] (2) preparing the aqueous phase: adding polyvinyl alcohol and hexamethylenetetramine to water, stirring evenly, then adding a surfactant, adding an inorganic acid to adjust the pH to 2, stirring evenly to obtain an aqueous phase, wherein the amount of polyvinyl alcohol added is 2.2% of the mass of water, the amount of hexamethylenetetramine added is 2.2% of the mass of water, and the amount of surfactant added is 0.35% of the mass of water; the surfactant is propylene glycol fatty acid ester.

[0045] (3) preparing an oil phase: taking the following raw materials by mass fraction: 82% of an organic long-chain alcohol, 15% of octylamine (TOA), and 3% of Span 85, and mixing them evenly to obtain an oil phase; the organic long-chain alcohol is n-decane;

[0046] (4) preparing an extraction solution: taking raw materials including the following mass fractions: 82% of an organic short-chain alcohol, 15% of octylamine (TOA), and 3% of Span 85, and mixing them evenly to obtain an extraction solution; the organic short-chain alcohol is isobutane;

[0047] (5) The initial phase solution, the water phase, and the oil phase are loaded into a coaxial needle tube, the center of the coaxial needle tube is the initial phase solution, the second outer layer is the water phase, and the outermost layer is the oil phase, so that the three solutions meet at the same point in layers, and the flow rate ratio of the initial phase solution to the water phase, and the initial phase solution to the oil phase is controlled. The flow rate ratio of the initial phase solution to the water phase is 0.6, and the flow rate ratio of the initial phase solution to the oil phase is 0.2. The flow rate of the oil phase is greater than the flow rate of the water phase. The flow rate of the initial phase solution is 0.3 mL / min, so that the emulsion droplets dispersed in the oil phase solution at the outlet of the coaxial needle tube are continuous spherical emulsion droplets, and the outlet tube is placed in a water bath environment at 85° C.;

[0048] (6) dropping the liquid out of the tube into the extraction solution for extraction and solidification to obtain an extract containing microspheres, and placing the extract in a water bath at 78° C.;

[0049] (7) The extract containing microspheres is subjected to reduced pressure fractionation to recover the oil phase, and vacuum drying is performed to obtain microsphere blanks; the microsphere blanks are fired at the firing temperature of the metal oxide of the metal alkoxide to obtain the finished product; the particle size of the microspheres is 150-200 μm, and the sphericity is 95%.

[0050] Example 3: A liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis, comprising the following steps:

[0051] (1) Preparing an initial phase solution: taking the following raw materials by mass fraction: 94% of liquid metal alkoxide, 5% of tetraethyl orthosilicate, and 1% of glass phase, and blending and dispersing them to obtain an initial phase solution; the liquid metal alkoxide is tetraethyl titanate; the glass phase is barium oxide, and the powder fineness of the glass phase is D98 <1.1 μm.

[0052] (2) preparing the aqueous phase: adding polyvinyl alcohol and hexamethylenetetramine to water, stirring evenly, then adding a surfactant, adding an inorganic acid to adjust the pH to 2, stirring evenly to obtain an aqueous phase, wherein the amount of polyvinyl alcohol added is 2.5% of the mass of water, the amount of hexamethylenetetramine added is 2.5% of the mass of water, and the amount of surfactant added is 0.4% of the mass of water; the surfactant is glyceryl monostearate.

[0053] (3) preparing an oil phase: taking the following raw materials by mass fraction: 85% of an organic long-chain alcohol, 10% of octylamine (TOA), and 5% of Span 85, and mixing them evenly to obtain an oil phase; the organic long-chain alcohol is n-decane;

[0054] (4) preparing an extraction solution: taking raw materials including the following mass fractions: 85% of an organic short-chain alcohol, 10% of octylamine (TOA), and 5% of Span 85, and mixing them evenly to obtain an extraction solution; the organic short-chain alcohol is n-butane;

[0055] (5) The initial phase solution, the water phase, and the oil phase are loaded into a coaxial needle tube, the center of the coaxial needle tube is the initial phase solution, the second outer layer is the water phase, and the outermost layer is the oil phase, so that the three solutions meet at the same point in layers, and the flow rate ratio of the initial phase solution to the water phase, and the initial phase solution to the oil phase is controlled. The flow rate ratio of the initial phase solution to the water phase is 0.8, the flow rate ratio of the initial phase solution to the oil phase is 0.5, the flow rate of the oil phase is greater than the flow rate of the water phase, and the flow rate of the initial phase solution is 0.4 mL / min, so that the emulsion droplets dispersed in the oil phase solution at the outlet of the coaxial needle tube are continuous spherical emulsion droplets, and the outlet tube is placed in a 90° C. water bath environment;

[0056] (6) dropping the liquid out of the tube into the extraction solution for extraction and solidification to obtain an extract containing microspheres, and placing the extract in a water bath at 85° C.;

[0057] (7) The extract containing microspheres is subjected to reduced pressure fractionation to recover the oil phase, and vacuum drying is performed to obtain microsphere blanks; the microsphere blanks are fired at the firing temperature of the metal oxide of the metal alkoxide to obtain the finished product; the particle size is 220 to 250 μm, and the sphericity is 96%.

[0058] Example 4: A liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis, comprising the following steps:

[0059] (1) Preparing an initial phase solution: taking the following raw materials by mass fraction: 96% of liquid metal alkoxide, 4% of tetraethyl orthosilicate, and 2% of glass phase, and blending and dispersing them to obtain an initial phase solution; the liquid metal alkoxide is aluminum sec-butylate; the glass phase is calcium carbonate, and the powder fineness of the glass phase is D98 <1.1 μm.

[0060] (2) preparing the aqueous phase: adding polyvinyl alcohol and hexamethylenetetramine to water, stirring evenly, then adding a surfactant, adding an inorganic acid to adjust the pH to 2, stirring evenly to obtain an aqueous phase, wherein the amount of polyvinyl alcohol added is 3% of the mass of water, the amount of hexamethylenetetramine added is 3% of the mass of water, and the amount of surfactant added is 0.5% of the mass of water; the surfactant is propylene glycol fatty acid ester.

[0061] (3) preparing an oil phase: taking raw materials including the following mass fractions: 80% of an organic long-chain alcohol, 16% of octylamine (TOA), and 4% of Span 85, and mixing them evenly to obtain an oil phase; the organic long-chain alcohol is n-decane;

[0062] (4) preparing an extraction solution: taking raw materials including the following mass fractions: 80% of an organic short-chain alcohol, 16% of octylamine (TOA), and 4% of Span 85, and mixing them evenly to obtain an extraction solution; the organic short-chain alcohol is n-butane;

[0063] (5) The initial phase solution, the water phase, and the oil phase are loaded into a coaxial needle tube, the center of the coaxial needle tube is the initial phase solution, the second outer layer is the water phase, and the outermost layer is the oil phase, so that the three solutions meet at the same point in layers, and the flow rate ratio of the initial phase solution to the water phase, and the initial phase solution to the oil phase is controlled. The flow rate ratio of the initial phase solution to the water phase is 1, and the flow rate ratio of the initial phase solution to the oil phase is 0.7. The flow rate of the oil phase is greater than the flow rate of the water phase. The flow rate of the initial phase solution is 0.5 mL / min, so that the emulsion droplets dispersed in the oil phase solution at the outlet of the coaxial needle tube are continuous spherical emulsion droplets, and the outlet tube is placed in a 95° C. water bath environment;

[0064] (6) dropping the liquid out of the tube into the extraction solution for extraction and solidification to obtain an extract containing microspheres, and placing the extract in a water bath at 90° C.;

[0065] (7) fractionating the extract containing the microspheres under reduced pressure to recover the oil phase, and vacuum drying to obtain microsphere blanks; and sintering the microsphere blanks at the sintering temperature of the metal oxide of the metal alkoxide to obtain the finished product;

[0066] The particle size is between 330 and 360 μm, and the sphericity is 99%.

[0067] Example 5: Referring to Example 1, the chemical formula of the liquid metal alkoxide is M m (OC x H y ) n, M is a metal element, the value of x is <5, the liquid metal alkoxide is a combination of one or more liquid metal alkoxides; the glass phase is an oxide or carbonate of calcium, magnesium, or barium, and the powder fineness of the glass phase is D98 <1.1 μm. The hydrophile-lipophile balance (HLB) value of the surfactant is between 3 and 8. The flow rate of the initial phase solution is not greater than 0.5 mL / min, so that the emulsion droplets dispersed in the oil phase solution by the coaxial needle outlet tube are continuous spherical emulsion droplets.

[0068] The described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis, characterized in that: The following steps are involved: (1) preparing an initial phase solution: taking raw materials including the following mass fractions: 92-95% of liquid metal alkoxide, 2-5% of tetraethyl orthosilicate, and 1-3% of glass phase, and blending and dispersing them to obtain an initial phase solution; (2) preparing an aqueous phase: adding polyvinyl alcohol and hexamethylenetetramine to water, stirring evenly, then adding a surfactant, adding an inorganic acid to adjust the pH to 2, stirring evenly to obtain an aqueous phase, wherein the amount of polyvinyl alcohol added is 2-3% of the mass of water, the amount of hexamethylenetetramine added is 2-3% of the mass of water, and the amount of the surfactant added is 0.3-0.5% of the mass of water; (3) preparing the oil phase: taking the following raw materials by mass fraction: 75-85% of an organic long carbon chain alcohol, 10-20% of TOA, and 3-5% of Span 85, and mixing them uniformly to obtain an oil phase; (4) preparing an extraction solution: taking raw materials including the following mass fractions: 75-85% of an organic short-chain alcohol, 10-20% of TOA, and 3-5% of Span 85, and mixing them uniformly to obtain an extraction solution; (5) loading the initial phase solution, the water phase, and the oil phase into a coaxial needle tube, wherein the center of the coaxial needle tube is the initial phase solution, the second outer layer is the water phase, and the outermost layer is the oil phase, and the flow rate ratios of the initial phase solution to the water phase, and the initial phase solution to the oil phase are controlled so that the emulsion droplets dispersed in the oil phase solution at the outlet of the coaxial needle tube are continuous spherical emulsion droplets, and the outlet tube is placed in a water bath environment at 80 to 95° C.; (6) dropping the liquid out of the tube into the extraction solution for extraction and solidification to obtain an extract containing microspheres, and placing the extract in a water bath at 75 to 90° C.; (7) Recovering the oil phase from the extract containing the microspheres by vacuum distillation, and obtaining microsphere blanks by vacuum drying; and calcining the microsphere blanks at the calcination temperature of the metal oxide of the metal alkoxide to obtain the finished product.

2. The liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis according to claim 1, characterized in that: The chemical formula of the liquid metal alkoxide is M m (OC x H y ) n , M is a metal element, the value of x is <5, and the liquid metal alkoxide is a combination of one or more liquid metal alkoxides.

3. The liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis according to claim 1, characterized in that: The glass phase is oxides or carbonates of calcium, magnesium and barium, and the powder fineness of the glass phase is D98<1.1 μm.

4. The liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis according to claim 1, characterized in that: The hydrophile-lipophile balance (HLB) value of the surfactant in step (2) is in the range of 3 to 8.

5. The liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis according to claim 4, characterized in that: The surfactant in step (2) is glyceryl monostearate or propylene glycol fatty acid ester.

6. The liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis according to claim 1, characterized in that: The longest carbon chain of the organic long-chain alcohol in step (3) is greater than 9, and the longest carbon chain of the organic short-chain alcohol in step (4) is less than 5.

7. The liquid forming method for preparing ceramic microspheres by alkoxide hydrolysis according to claim 1, characterized in that: The flow rate ratio of the initial phase solution to the water phase is 0.5-1, the flow rate ratio of the initial phase solution to the oil phase is 0.1-0.7, the flow rate of the oil phase is greater than the flow rate of the water phase, and the flow rate of the initial phase solution is not greater than 0.5 mL / min.

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