Ceramic hollow microsphere precursor solution preparation device and use method thereof

Abstract

The invention discloses a ceramic hollow microsphere precursor solution preparation device and a use method thereof. The invention relates to a preparation device of a ceramic hollow microsphere precursor solution. The preparation device comprises a liquid phase temperature control reaction tank, a condenser, a pressure buffer tank and a vacuum pump, wherein the liquid phase temperature control reaction tank is connected with the condenser through a first gas pipeline and a first liquid pipeline; the condenser is connected with the pressure buffer tank through a second gas pipeline; the pressure buffer tank is connected with the vacuum pump; the liquid phase temperature control reaction tank is provided with a temperature control device and a stirring device, and the temperature control device and the stirring device are connected with the central control device through an electric connection device; and the liquid phase temperature control reaction tank is connected with the feeding power device through a second liquid pipeline. The prepared nitride ceramic microspheres are small in particle size and resistant to high temperature, a large number of organic solvents do not need to be adopted in the preparation process, environmental pollution is avoided, the cost is low, and therefore industrial production can be achieved.

Description

Technical Field

[0001] The invention relates to the technical field of a ceramic hollow microsphere precursor solution preparation device, and in particular to the field of a ceramic hollow microsphere precursor solution preparation device and a use method thereof. Background Art

[0002] Ceramic hollow microspheres have a hollow structure and are often used as functional materials, especially nitride ceramic microspheres, which are more widely used and have been widely used in aerospace, stealth, storage and other fields.

[0003] Nitride ceramic microspheres are usually prepared from precursors, which are widely prepared by liquid phase template method or hydrothermal method. The prepared nitride ceramic microspheres are amorphous in structure and have low high temperature resistance during use, which affects their promotion and application. The applicant tried to solve this problem in the research of nitride ceramic microsphere project. However, due to the limitation that most of the devices for preparing precursor solutions on the market are suitable for liquid phase template method or hydrothermal method, they cannot be used to prepare suitable precursor solutions, thereby solving the problem that nitride ceramic microspheres are amorphous in structure and have low high temperature resistance.

[0004] Therefore, the art urgently needs a new preparation device for ceramic hollow microsphere precursor solution and its use method, so as to prepare a new ceramic hollow microsphere precursor solution to solve the problem that nitride ceramic microspheres have an amorphous structure and low high temperature resistance. Summary of the invention

[0005] The purpose of the present invention is to provide a ceramic hollow microsphere precursor liquid preparation device and a use method thereof, so that the prepared nitride ceramic microspheres have a small particle size and high temperature resistance, do not need to use a large amount of organic solvents during the preparation process, avoid environmental pollution and have low costs, thereby realizing industrial production.

[0006] According to one aspect of the present invention, there is provided a ceramic hollow microsphere precursor solution preparation device, comprising: a liquid phase temperature control reaction tank, a condenser, a pressure buffer tank, and a vacuum pump;

[0007] The liquid phase temperature control reaction tank is connected to the condenser through a first gas pipeline and a first liquid pipeline;

[0008] The condenser is connected to the pressure buffer tank through a second gas pipeline; the pressure buffer tank is connected to the vacuum pump;

[0009] The liquid phase temperature control reaction tank is provided with a temperature control device and a stirring device, and the temperature control device and the stirring device are connected to the central control device through an electrical connection device;

[0010] The liquid-phase temperature-controlled reaction tank is connected to a feed power device via a second liquid pipeline; preferably, the feed power device is a delivery pump.

[0011] The beneficial effect of the present invention compared with the prior art is that the prepared raw materials are fed into the liquid phase temperature control reaction tank through the second liquid pipeline; the temperature of the materials in the liquid phase temperature control reaction tank is controlled by the temperature control device to control the reaction of the materials;

[0012] The liquid-phase temperature-controlled reaction tank is connected to the condenser through the first gas pipeline and the first liquid pipeline, so that the material in the liquid-phase temperature-controlled reaction tank is in a negative pressure state, and the material reacts in the negative pressure environment. At the same time, the material in the gas extracted from the liquid-phase temperature-controlled reaction tank is cooled to a liquid state through the condenser and then flows back to the liquid-phase temperature-controlled reaction tank through the first liquid pipeline, so that the concentration and proportion of the materials remain unchanged under the negative pressure environment, and the ceramic substrate components attached to the surface of the microcapsules in the formed ceramic hollow microsphere precursor are avoided. The uniform distribution and thickness of the ceramic substrate components attached to the surface of the microcapsules are basically consistent, and it is also beneficial to protect the vacuum pump and prevent the problem of excessive humidity of the gas entering the vacuum pump; the condenser is connected to the pressure buffer tank through the second gas pipeline to achieve stable pressure in the liquid-phase temperature-controlled reaction tank, and protect the vacuum pump, so as to avoid the instability of the vacuum pump caused by the high humidity of the gas entering the vacuum pump;

[0013] Through negative pressure reaction conditions, the final finished ceramic microspheres can withstand high temperatures of more than 1960°C during use, and preferably, the use temperature can reach more than 1980°C.

[0014] Furthermore, the stirring device comprises a stirring rod extending into the liquid phase temperature control reaction tank and a first stirring blade and a second stirring blade arranged on the stirring rod;

[0015] The first stirring blade is a propeller blade axially wound around the stirring rod, and the second stirring blade is an anchor blade connected to the end of the stirring rod;

[0016] and / or

[0017] The condenser is provided with a spirally distributed condensation pipeline inside, and a gas-liquid separation membrane system is also provided inside the condenser.

[0018] The beneficial effect of adopting the above technical solution is that the first stirring blade is a propeller blade wound on the stirring rod, and the second stirring blade is an anchor blade connected to the stirring rod, which is conducive to the formation of microcapsules during the stirring process and is also conducive to the rupture of the formed microcapsules due to stirring, that is, the anchor blade located at the bottom is easy to form microcapsules during the stirring process, and the propeller blade at the top is only conducive to the movement of the microcapsules in the solution with the formed liquid flow, and will not cause the microcapsules to rupture;

[0019] The spirally distributed condensation pipeline in the condenser is conducive to condensing the material in the passing gas into liquid; the gas-liquid separation membrane system is conducive to separating the generated liquid and the components maintained in the gaseous state.

[0020] Furthermore, a partition is provided in the liquid phase temperature control reaction tank, and the partition is provided with a plurality of through holes;

[0021] The partition separates the liquid phase temperature control reaction tank into an upper body of the liquid phase temperature control reaction tank and a lower body of the liquid phase temperature control reaction tank; after the material in the liquid phase temperature control reaction tank is added, the material is located in the lower body of the liquid phase temperature control reaction tank, and the partition is located above the material.

[0022] The beneficial effect of adopting the previous technical solution is that by dividing the liquid-phase temperature-controlled reaction tank into an upper body of the liquid-phase temperature-controlled reaction tank and a lower body of the liquid-phase temperature-controlled reaction tank, it is beneficial to realize the reaction of the material in the reaction tank at a certain temperature and under a negative pressure environment, and it is also beneficial to control the temperature of the space without material to be different from the temperature of the space with material, thereby realizing the overall negative pressure in the tank body while avoiding the gas extracted from the tank body from carrying material; a number of through holes are provided through the partition, so that when the upper body of the liquid-phase temperature-controlled reaction tank is evacuated, a negative pressure state is also achieved in the lower body of the liquid-phase temperature-controlled reaction tank, and it is also beneficial for the material condensed in the upper body of the liquid-phase temperature-controlled reaction tank to continue to flow back to the lower body of the liquid-phase temperature-controlled reaction tank when evacuating.

[0023] Furthermore, the temperature control device includes a first temperature control device and a second temperature control device, wherein the first temperature control device is connected to the upper body of the liquid-phase temperature control reaction tank, and the second temperature control device is connected to the lower body of the liquid-phase temperature control reaction tank.

[0024] Furthermore, the stirring rod extends from the upper body of the liquid phase temperature control reaction tank through the partition into the lower body of the liquid phase temperature control reaction tank, and the first stirring blade and the second stirring blade are arranged on the stirring rod located on the lower body of the liquid phase temperature control reaction tank.

[0025] The beneficial effect of adopting the previous technical solution is that by controlling the temperature inside the upper body of the liquid-phase temperature-controlled reaction tank through the first temperature control device, its temperature can be kept low, which is beneficial to avoid the material in the tank being drawn out with the gas during vacuuming; and by controlling the material in the lower body of the liquid-phase temperature-controlled reaction tank through the second temperature control device, the temperature required for the reaction is met under a negative pressure environment.

[0026] Furthermore, the partition is tilted, and the angle between the partition and the horizontal plane is 10-30°; preferably, the partition includes a metal body and a coating connected to the inner surface of the main body of the liquid phase temperature control reaction tank, and the coating is made of polytetrafluoroethylene; the first gas pipeline inlet is located at one end of the partition that is higher than the midpoint horizontal plane.

[0027] The beneficial effect of adopting the above technical solution is that the partition is inclined, which is conducive to preventing the material from being easily drawn out during vacuuming, and is conducive to the small amount of drawn material condensing in the upper body of the liquid phase temperature control reaction tank and then flowing back into the lower body of the liquid phase temperature control reaction tank;

[0028] The partition includes a metal body and a coating connected to the inner surface of the upper body of the liquid-phase temperature-controlled reaction tank. The coating is made of polytetrafluoroethylene, which is beneficial to isolating the temperature inside the upper body of the liquid-phase temperature-controlled reaction tank from the temperature inside the lower body of the liquid-phase temperature-controlled reaction tank. At the same time, the metal surface of the partition is beneficial to the gas extracted from the lower body of the liquid-phase temperature-controlled reaction tank to partially condense and remain in the lower body of the liquid-phase temperature-controlled reaction tank when passing through the metal surface of the partition. At the same time, the coating is made of polytetrafluoroethylene, which is beneficial to avoiding the problem of liquid condensed from the upper body of the liquid-phase temperature-controlled reaction tank adhering to the partition, and is also beneficial to achieving isolated temperature.

[0029] Furthermore, the second liquid pipeline extends into the liquid phase temperature control reaction tank, and the liquid outlet of the second liquid pipeline is located below the liquid surface of the material;

[0030] The first gas pipeline does not extend into the interior of the liquid phase temperature control reaction tank;

[0031] The first liquid pipeline extends into the liquid phase temperature control reaction tank, and the liquid outlet of the first liquid pipeline is connected to a protective cover body.

[0032] The beneficial effect of adopting the above technical solution is that the outlet of the second liquid pipeline is located below the liquid surface of the material, which helps to prevent the added raw materials from not being able to completely enter the lower body of the liquid phase temperature control reaction tank;

[0033] The first liquid pipeline extends into the liquid phase temperature control reaction tank, and the first liquid pipeline outlet is connected to a protective cover body, which is helpful to prevent the refluxed condensate from being sucked away when vacuuming during the falling process.

[0034] Further, the liquid phase temperature control reaction tank is located below the condenser, the condenser is tilted, the condenser liquid outlet is located on the lower surface of one end of the condenser tilted upward, the air outlet is located on the upper surface of one end of the condenser tilted upward, and the air inlet is located on the lower surface of one end of the condenser tilted downward;

[0035] The liquid outlet of the condenser is connected to the first liquid pipeline; the gas outlet of the condenser is connected to the second gas pipeline; and the gas inlet of the condenser is connected to the first gas pipeline.

[0036] The beneficial effect of adopting the previous technical solution is that it is conducive to achieving the movement of the gas extracted from the liquid phase temperature control reaction tank from bottom to top when passing through the condenser, thereby improving the condensation efficiency and facilitating the separation of the condensate and the gas.

[0037] According to another aspect of the present invention, there is provided a method for using a ceramic hollow microsphere precursor solution preparation device, comprising the following steps: adding water into a liquid-phase temperature-controlled reaction tank through a second liquid pipeline by a feed power device, and controlling the temperature control device by a central control device to heat the water in the liquid-phase temperature-controlled reaction tank;

[0038] Then, an emulsifier is added to the liquid phase temperature control reaction tank through the second liquid pipeline, and the stirring device is turned on and stirred for 12-20 minutes; then, a nitrogen-containing compound is added through the second liquid pipeline, stirring is continued for a certain period of time, stirring is stopped, and the mixture is allowed to stand;

[0039] Add the ceramic substrate component into the liquid-phase temperature control reaction tank through the second liquid pipeline, then start the vacuum pump, and draw part of the gas in the liquid-phase temperature control reaction tank into the condenser and the pressure buffer tank in sequence through the second gas pipeline and the first gas pipeline, so that the liquid-phase temperature control reaction tank is in a negative pressure state, and the negative pressure is -0.1MPa to -0.01MPa; and continue to start stirring at the same time;

[0040] The material contained in the gas is condensed by the condenser and becomes liquid, and then flows into the liquid phase temperature control reaction tank through the first liquid pipeline;

[0041] Then, a surfactant is added to the liquid phase temperature-controlled reaction tank through a second liquid pipeline to obtain a ceramic hollow microsphere precursor solution; preferably, the ceramic substrate component includes one or more of metal chlorides, metal nitrates, and metal sulfates; preferably, the ratio of water to emulsifier is (55-75): (0.3-0.45); the mass ratio of the ceramic substrate component, the nitrogen-containing compound and water is (10-15): (15-30): (55-75); the surfactant accounts for 0.05%-0.25% of the mass of the ceramic substrate component.

[0042] Compared with the prior art, the beneficial effects of the present invention are that water and an emulsifier are added to a liquid-phase temperature-controlled reaction tank respectively through a second liquid pipeline; the temperature of the material in the liquid-phase temperature-controlled reaction tank is controlled by a temperature control device to control the reaction of the material, thereby facilitating the emulsifier to form emulsified vesicles with a stable hollow spherical structure; the nitrogen-containing compound is added and stirred, so that the nitrogen-containing compound is uniformly attached to the surface of the emulsified vesicle, and the pH value of the solution is adjusted to 8-9; the nitrogen-containing compound is made to have a high binding strength on the surface of the emulsified vesicle, and then the nitrogen-containing compound is combined with the emulsifier through a primary pre-reaction to obtain a nitrogen-based emulsifier by standing, and then the emulsifier vesicles are ruptured and the nitrogen-based emulsifier is uniformly dispersed in water to obtain a nitrogen-based emulsifier solution.

[0043] The nitrogen-based emulsifier solution includes a solvent and an emulsifier, and the solvent is water, thereby avoiding the problem of environmental pollution and high cost caused by the organic solvent;

[0044] The ceramic substrate component is added to the nitrogen-based emulsifier solution and then stirred at a high speed, thereby obtaining nitrogen-containing emulsified vesicles in water, wherein the ceramic substrate component is evenly distributed on the surface of the nitrogen-containing emulsified vesicles, and the pH is adjusted through a secondary pre-reaction to achieve a higher bonding strength between the nitrogen-containing compound and the ceramic substrate component than between the nitrogen-containing compound and the emulsifier; and a surfactant is added to form surfactant microspheres with a non-polar interior and a non-polar exterior in water, thereby achieving uniform dispersion of the ceramic-based composite nitrogen element emulsified vesicles between the surfactant microspheres, which is further conducive to achieving the ceramic-based composite nitrogen element emulsified vesicles. The ceramic-based composite nitrogen emulsified vesicles include ceramic-based composite nitrogen microcapsules and emulsifier vesicles attached to the inside of the ceramic-based composite nitrogen microcapsules. The surfactant microspheres are beneficial to avoiding the rupture of the ceramic-based composite nitrogen microcapsules, thereby improving their strength. It is also beneficial to achieving small and uniform ceramic-based composite nitrogen microcapsules, and achieving partial or complete rupture of the emulsifier vesicles and dispersion into water, but the ceramic-based composite nitrogen microcapsules are not damaged and remain intact. This is also beneficial to avoiding the problem of increased porosity on the surface of nitride ceramic microspheres caused by the large amount of volatilization of the emulsifier during subsequent drying and sintering, thereby avoiding the reduction of the density of the surface of the nitride ceramic microspheres.

[0045] By preparing a nitride ceramic microsphere precursor solution, the ceramic substrate component added includes one or more of metal chloride, metal nitrate, and metal sulfate, and the ceramic base component does not include organic salt, thereby avoiding the problem of reduced strength of the ceramic microspheres caused by non-volatilization of organic matter in the subsequent sintering process;

[0046] The liquid-phase temperature-controlled reaction tank is connected to the condenser through the first gas pipeline and the first liquid pipeline, so that the material in the liquid-phase temperature-controlled reaction tank is in a negative pressure state, and the material reacts in the negative pressure environment. At the same time, the material in the gas extracted from the liquid-phase temperature-controlled reaction tank is cooled to a liquid state through the condenser and then flows back to the liquid-phase temperature-controlled reaction tank through the first liquid pipeline, so that the concentration and proportion of the materials remain unchanged under the negative pressure environment, and the ceramic substrate components attached to the surface of the microcapsules in the formed ceramic hollow microsphere precursor are avoided. The uniform distribution and thickness of the ceramic substrate components attached to the surface of the microcapsules are basically consistent, and it is also beneficial to protect the vacuum pump and prevent the problem of excessive humidity of the gas entering the vacuum pump; the condenser is connected to the pressure buffer tank through the second gas pipeline to achieve stable pressure in the liquid-phase temperature-controlled reaction tank, and protect the vacuum pump, so as to avoid the instability of the vacuum pump caused by the high humidity of the gas entering the vacuum pump;

[0047] Through negative pressure reaction conditions, the final finished ceramic microspheres can withstand high temperatures of more than 1960°C during use, and preferably, the use temperature can reach more than 1980°C.

[0048] Furthermore, the method for using the ceramic hollow microsphere precursor solution preparation device specifically includes the following steps: adding water into the lower body of the liquid phase temperature control reaction tank through the second liquid pipeline by the feeding power device, and controlling the second temperature control device by the central control device to heat the water in the liquid phase temperature control reaction tank;

[0049] Then, an emulsifier is added into the lower body of the liquid phase temperature control reaction tank through the second liquid pipeline;

[0050] Add the ceramic substrate component into the lower body of the liquid-phase temperature-controlled reaction tank through the second liquid pipeline; then open the first temperature control device connected to the upper body of the liquid-phase temperature-controlled reaction tank to cool the upper body of the liquid-phase temperature-controlled reaction tank to control the temperature at 15-20°C;

[0051] The second temperature control device heats the material in the lower body of the liquid phase temperature control reaction tank, and the temperature is controlled at 40-60°C.

[0052] The beneficial effect of adopting the above technical solution is that the temperature in the upper body of the liquid-phase temperature-controlled reaction tank can be controlled by the first temperature control device, so that the temperature can be kept low, which is beneficial to prevent the material in the tank from being drawn out with the gas during vacuuming; the material in the lower body of the liquid-phase temperature-controlled reaction tank is controlled by the second temperature control device to meet the temperature required for the reaction under a negative pressure environment;

[0053] The finally obtained ceramic hollow microspheres have a submicron hollow spherical structure;

[0054] The particle size of the ceramic hollow microspheres is 0.05-20 μm, the wall thickness of the nitride ceramic microspheres is 10-25 nm, and the bulk density of the ceramic hollow microspheres is 0.25-0.4 g / cm 3 ; The crushing strength of the ceramic hollow microspheres that account for 5% of the volume is 58-75MPa; Preferably, the particle size of the ceramic hollow microspheres is 0.05-0.09μm, and the crushing strength of the ceramic hollow microspheres that account for 5% of the volume is 58-68MPa. The crushing strength of the ceramic hollow microspheres that account for 5% of the volume means the pressure strength when 5% of the volume of the ceramic hollow microspheres is crushed when the ceramic hollow microspheres are tested. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be described below.

[0056] Figure 1 This is a schematic structural diagram of a device for preparing a ceramic hollow microsphere precursor solution according to Example 1 of the present invention;

[0057] Figure 2 This is an electron microscope picture of the nitride ceramic microspheres of the present invention.

[0058] Markings shown in the accompanying drawings:

[0059] 1. Liquid phase temperature control reaction tank; 2. Condenser; 3. Pressure buffer tank; 4. Vacuum pump; 5. Feed power device; 6. Central control device; 7. Electrical connection device; 8. First gas pipeline; 9. First liquid pipeline; 10. Second gas pipeline; 11. Protective cover; 12. Third gas pipeline; 13. Second liquid pipeline; 14. First temperature control device; 15. Second temperature control device 16. Stirring rod; 17. Second stirring blade; 18. First stirring blade; 19. Partition. DETAILED DESCRIPTION

[0060] In order to better understand the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and the accompanying drawings of the specification.

[0061] Embodiment 1:

[0062] In one aspect of the present embodiment, a ceramic hollow microsphere precursor solution preparation device is provided, comprising: a liquid phase temperature control reaction tank 1, a condenser 2, a pressure buffer tank 3, and a vacuum pump 4, wherein the liquid phase temperature control reaction tank 1 is connected to the condenser 2 via a first gas pipeline 8 and a first liquid pipeline 9;

[0063] The condenser is connected to the pressure buffer tank 3 through the second gas pipeline 10; the pressure buffer tank 3 is connected to the vacuum pump 4, and specifically the pressure buffer tank is connected to the vacuum pump 4 through the third gas pipeline 12;

[0064] The liquid-phase temperature-controlled reaction tank 1 is provided with a temperature control device and a stirring device, and the temperature control device and the stirring device are connected to the central control device 6 via an electrical connection device; the electrical connection device is a wire; the liquid-phase temperature-controlled reaction tank 1 is connected to the feeding power device 5 via a second liquid pipeline 13, and the feeding power device 5 is a delivery pump.

[0065] The liquid phase temperature control reaction tank 1 is provided with a partition 19, and the partition 19 is provided with a plurality of through holes;

[0066] The partition 19 separates the liquid-phase temperature-controlled reaction tank 1 into an upper body of the liquid-phase temperature-controlled reaction tank and a lower body of the liquid-phase temperature-controlled reaction tank; after the material in the liquid-phase temperature-controlled reaction tank 1 is added, the material is located in the lower body of the liquid-phase temperature-controlled reaction tank, and the partition 19 is located above the material;

[0067] The temperature control device includes a first temperature control device 14 and a second temperature control device 15, wherein the first temperature control device 14 is connected to the upper body of the liquid-phase temperature control reaction tank, and the second temperature control device 15 is connected to the lower body of the liquid-phase temperature control reaction tank;

[0068] The liquid phase temperature control reaction tank 1 is located below the condenser 2, the condenser 2 is tilted, the liquid outlet of the condenser 2 is located on the lower surface of one end of the condenser 2 tilted upward, the air outlet is located on the upper surface of one end of the condenser 2 tilted upward, and the air inlet is located on the lower surface of one end of the condenser 2 tilted downward;

[0069] The liquid outlet of the condenser 2 is connected to the first liquid pipeline 9; the gas outlet of the condenser 2 is connected to the second gas pipeline 10; the gas inlet of the condenser 2 is connected to the first gas pipeline 8;

[0070] The second liquid pipeline 13 extends into the liquid phase temperature control reaction tank 1, and the liquid outlet of the second liquid pipeline 13 is located below the liquid surface of the material;

[0071] The first gas pipeline 8 does not extend into the interior of the liquid phase temperature control reaction tank 1;

[0072] The first liquid pipeline 9 extends into the liquid-phase temperature-controlled reaction tank 1 , and a liquid outlet of the first liquid pipeline 9 is connected to a protective cover body 11 .

[0073] The stirring device comprises a stirring rod 16 extending into the liquid phase temperature control reaction tank 1 and a first stirring blade 18 and a second stirring blade 17 arranged on the stirring rod 16;

[0074] The first stirring blade 18 is a propeller blade axially wound around the stirring rod 16 , and the second stirring blade 17 is an anchor blade connected to the end of the stirring rod 16 .

[0075] In another aspect of the present embodiment, a method for using a ceramic hollow microsphere precursor solution preparation device is provided, comprising the following steps:

[0076] Water is added into the lower body of the liquid phase temperature control reaction tank through the second liquid pipeline 13 by the feed power device 5, and the second temperature control device 15 is controlled by the central control device to heat the water in the lower body of the liquid phase temperature control reaction tank; the temperature is controlled at 50°C;

[0077] Then, an emulsifier is added to the liquid phase temperature control reaction tank 1 through the second liquid pipeline 13, and the stirring device is turned on at a speed of 1350 r / min, and stirred for 16 minutes to form an emulsified vesicle with a stable hollow spherical structure, and a nitrogen-containing compound is added through the second liquid pipeline 13 and stirred for 10 minutes, and then the pH is adjusted to obtain a transparent white emulsified nitrogen-containing emulsified vesicle solution; the pH value of the solution is 8.5, and the stirring is stopped and the solution is allowed to stand, and a nitrogen-based emulsifier solution is obtained after a primary pre-reaction; the nitrogen-containing compounds are urea and melamine;

[0078] A ceramic substrate component is added into the liquid-phase temperature control reaction tank 1 through the second liquid pipeline 13, and then the vacuum pump 4 is turned on, and part of the gas in the liquid-phase temperature control reaction tank 1 is pumped into the condenser 2 and the pressure buffer tank 3 in sequence through the second gas pipeline 10 and the first gas pipeline 8, so that the liquid-phase temperature control reaction tank 1 is in a negative pressure state, and the negative pressure is -0.051 MPa; at the same time, stirring is continued at a speed of 1350 r / min to form nitrogen-based emulsified vesicles, and the pH is adjusted to obtain ceramic-based composite nitrogen element emulsified vesicles after secondary pre-reaction; a surfactant is added to obtain a nitride ceramic microsphere precursor solution; after the nitrogen-based emulsified vesicles are formed, the pH is adjusted to 7.2;

[0079] The ceramic substrate component includes metal chloride and metal nitrate; specifically, the metal chloride is aluminum chloride, and the metal nitrate is aluminum nitrate (aluminum nitrate nonahydrate); the ratio of water to emulsifier is 65:0.375; the mass ratio of the ceramic substrate component, the nitrogen-containing compound and water is 12:23:65; the surfactant accounts for 0.15% of the mass of the ceramic substrate component;

[0080] The extracted gas is condensed by the condenser 2, and the material contained in the gas is condensed by the condenser 2 and becomes liquid and flows into the liquid phase temperature control reaction tank 1 through the first liquid pipeline 9; the condensate temperature in the condensation device is 8°C;

[0081] Then, the surfactant is added into the lower tank body of the liquid phase temperature control reaction tank through the second liquid pipeline 13 to obtain a ceramic hollow microsphere precursor solution.

[0082] The finally obtained ceramic hollow microspheres have a submicron hollow spherical structure;

[0083] The use temperature of the ceramic hollow microspheres can reach 1965°C; the particle size of the ceramic hollow microspheres is 0.08 μm, the wall thickness of the nitride ceramic microspheres is 18 nm, and the bulk density of the ceramic hollow microspheres is 0.33 g / cm 3 ; The crushing strength of the ceramic hollow microspheres that account for 5% of the volume is 67MPa; the crushing strength of the ceramic hollow microspheres that account for 5% of the volume means the pressure strength when 5% of the volume of the ceramic hollow microspheres are crushed when the ceramic hollow microspheres are tested.

[0084] Embodiment 2:

[0085] The same contents as those in Example 1 are not described in detail here. The differences between this embodiment and Example 1 are as follows:

[0086] In one aspect of this embodiment, a device for preparing a ceramic hollow microsphere precursor solution is provided.

[0087] The condenser is provided with a spirally distributed condensation pipeline inside, and a gas-liquid separation membrane system is also provided inside the condenser.

[0088] The partition is arranged at an angle, and the angle between the partition and the horizontal plane is 20°; the partition includes a metal body and a coating connected to the inner surface of the main body of the liquid phase temperature control reaction tank, and the coating is made of polytetrafluoroethylene; the air inlet of the first gas pipeline 8 is located at one end of the partition that is higher than the midpoint horizontal plane.

[0089] In another aspect of the present embodiment, a method for using a ceramic hollow microsphere precursor solution preparation device is provided, comprising the following steps:

[0090] The central control device controls the second temperature control device 15 to heat the water in the lower body of the liquid phase temperature control reaction tank; the temperature is controlled at 45°C;

[0091] Then, an emulsifier is added to the liquid phase temperature control reaction tank 1 through the second liquid pipeline 13, and the stirring device is turned on at a speed of 1300 r / min and stirred for 18 minutes to form an emulsified vesicle with a stable hollow spherical structure. A nitrogen-containing compound is added through the second liquid pipeline 13 and stirred for 15 minutes, and then the pH is adjusted to obtain a transparent white emulsified nitrogen-containing emulsified vesicle solution; the solution pH value is 8.8, stirring is stopped, and the solution is allowed to stand, and a nitrogen-based emulsifier solution is obtained after a primary pre-reaction;

[0092] The negative pressure is -0.085 MPa; stirring is continued at a speed of 1300 r / min to form nitrogen-based emulsified vesicles, and the pH is adjusted to obtain ceramic-based composite nitrogen element emulsified vesicles after secondary pre-reaction; a surfactant is added to obtain a nitride ceramic microsphere precursor solution; after the nitrogen-based emulsified vesicles are formed, the pH is adjusted to 6.8;

[0093] The ceramic substrate components include metal nitrates and metal sulfates; specifically aluminum nitrate (aluminum nitrate nonahydrate) and calcium sulfate; the ratio of water to emulsifier is 72:0.35; the mass ratio of the ceramic substrate components, nitrogen-containing compounds and water is 13:19:61; the surfactant accounts for 0.1% of the mass of the ceramic substrate components;

[0094] The temperature of the condensate in the condensation device is 8° C.; the pressure of the negative pressure environment is -0.085 MPa.

[0095] The use temperature of the ceramic hollow microspheres can reach 1985°C; the particle size of the ceramic hollow microspheres is 0.07 μm, the wall thickness of the nitride ceramic microspheres is 20 nm, and the bulk density of the ceramic hollow microspheres is 0.38 g / cm 3 ; The crushing strength of 5% ceramic hollow microspheres is 73MPa.

[0096] The above description is only a preferred embodiment of the present application and an explanation of the technical principles used. Those skilled in the art should understand that the scope of the invention involved in the present application is not limited to the technical solution formed by a specific combination of the above technical features, but should also cover other technical solutions formed by any combination of the above technical features or their equivalent features without departing from the inventive concept. For example, the above features have similar functions to those disclosed in the present application (but not limited to).

Claims

1. A ceramic hollow microsphere precursor solution preparation device, characterized in that: include: Liquid phase temperature control reaction tank, condenser, pressure buffer tank, vacuum pump; The liquid phase temperature control reaction tank is connected to the condenser through a first gas pipeline and a first liquid pipeline; The condenser is connected to the pressure buffer tank through a second gas pipeline; the pressure buffer tank is connected to the vacuum pump; The liquid phase temperature control reaction tank is provided with a temperature control device and a stirring device, and the temperature control device and the stirring device are connected to the central control device through an electrical connection device; The liquid phase temperature control reaction tank is connected to the feed power device through a second liquid pipeline.

2. The ceramic hollow microsphere precursor solution preparation device according to claim 1, characterized in that: The stirring device comprises a stirring rod extending into the liquid phase temperature control reaction tank and a first stirring blade and a second stirring blade arranged on the stirring rod; The first stirring blade is a propeller blade axially wound around the stirring rod, and the second stirring blade is an anchor blade connected to the end of the stirring rod; and / or The condenser is provided with a spirally distributed condensation pipeline inside, and a gas-liquid separation membrane system is also provided inside the condenser.

3. The ceramic hollow microsphere precursor solution preparation device according to claim 2, characterized in that: A partition is provided in the liquid phase temperature control reaction tank, and the partition is provided with a plurality of through holes; The partition separates the liquid phase temperature control reaction tank into an upper body of the liquid phase temperature control reaction tank and a lower body of the liquid phase temperature control reaction tank; after the material in the liquid phase temperature control reaction tank is added, the material is located in the lower body of the liquid phase temperature control reaction tank, and the partition is located above the material.

4. The ceramic hollow microsphere precursor solution preparation device according to claim 3, characterized in that: The temperature control device comprises a first temperature control device and a second temperature control device, wherein the first temperature control device is connected to the upper body of the liquid-phase temperature control reaction tank, and the second temperature control device is connected to the lower body of the liquid-phase temperature control reaction tank.

5. The ceramic hollow microsphere precursor solution preparation device according to claim 3, characterized in that: The stirring rod extends from the upper body of the liquid phase temperature control reaction tank through the partition into the lower body of the liquid phase temperature control reaction tank, and the first stirring blade and the second stirring blade are arranged on the stirring rod located on the lower body of the liquid phase temperature control reaction tank.

6. The ceramic hollow microsphere precursor solution preparation device according to claim 3, characterized in that: The partition is tilted, and the angle between the partition and the horizontal plane is 10-30 degrees.

7. The ceramic hollow microsphere precursor solution preparation device according to claim 3, characterized in that: The second liquid pipeline extends into the liquid phase temperature control reaction tank, and the liquid outlet of the second liquid pipeline is located below the material liquid surface; The first gas pipeline does not extend into the interior of the liquid phase temperature control reaction tank; The first liquid pipeline extends into the liquid phase temperature control reaction tank, and the liquid outlet of the first liquid pipeline is connected to a protective cover body.

8. The ceramic hollow microsphere precursor solution preparation device according to claim 1, characterized in that: The liquid phase temperature control reaction tank is located below the condenser, the condenser is tilted, the condenser liquid outlet is located on the lower surface of one end of the condenser tilted upward, the air outlet is located on the upper surface of one end of the condenser tilted upward, and the air inlet is located on the lower surface of one end of the condenser tilted downward; The liquid outlet of the condenser is connected to the first liquid pipeline; the gas outlet of the condenser is connected to the second gas pipeline; The condenser air inlet is connected to the first gas pipeline.

9. A method for using a ceramic hollow microsphere precursor solution preparation device, comprising the following steps: The feed power device is used to add water into the liquid phase temperature control reaction tank through the second liquid pipeline, and the temperature control device is controlled by the central control device to heat the water in the liquid phase temperature control reaction tank; Then, an emulsifier is added to the liquid phase temperature control reaction tank through the second liquid pipeline, and the stirring device is turned on. After stirring for 12-20 minutes, stirring is stopped and the reaction tank is allowed to stand. Then, a nitrogen-containing compound is added through the second liquid pipeline, stirring is continued for a certain period of time, stirring is stopped and the reaction tank is allowed to stand. Add the ceramic substrate component into the liquid-phase temperature control reaction tank through the second liquid pipeline, then start the vacuum pump, and draw part of the gas in the liquid-phase temperature control reaction tank into the condenser and the pressure buffer tank in sequence through the second gas pipeline and the first gas pipeline, so that the liquid-phase temperature control reaction tank is in a negative pressure state, and the negative pressure is -0.1MPa to -0.01MPa; and continue to start stirring at the same time; The material contained in the gas is condensed by the condenser and becomes liquid, and then flows into the liquid phase temperature control reaction tank through the first liquid pipeline; Then, a surfactant is added into the liquid phase temperature control reaction tank through the second liquid pipeline to obtain a ceramic hollow microsphere precursor solution.

10. The method for using the ceramic hollow microsphere precursor solution preparation device according to claim 9, specifically comprising the following steps: The feed power device is used to add water into the lower body of the liquid-phase temperature-controlled reaction tank through the second liquid pipeline, and the central control device is used to control the second temperature control device to heat the water in the liquid-phase temperature-controlled reaction tank; Then, an emulsifier is added into the lower body of the liquid phase temperature control reaction tank through the second liquid pipeline; Add the ceramic substrate component into the lower body of the liquid-phase temperature-controlled reaction tank through the second liquid pipeline; then open the first temperature control device connected to the upper body of the liquid-phase temperature-controlled reaction tank to cool the upper body of the liquid-phase temperature-controlled reaction tank to control the temperature at 15-20°C; The second temperature control device heats the material in the lower body of the liquid phase temperature control reaction tank, and the temperature is controlled at 40-60°C.

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