Method for preparing high-pressure low-melting-point brittle porous ceramic texture material through photocuring compounding

Abstract

The invention belongs to the technical field of porous ceramic composite materials, and particularly relates to a design for preparing a high-pressure low-melting-point brittle porous ceramic texture material through photocuring compounding. When the valve element is applied to the safety valve of the vehicle-mounted hydrogen storage tank and the pressure in the hydrogen storage tank is too high, the brittle ceramic texture serves as a framework to be brittle and broken, the valve element moves, and gas is released; when the environment temperature rises, the cast low-melting-point tin-indium-bismuth alloy is melted instantly, gas is released from ceramic texture gaps, and the safe pressure of the hydrogen storage tank is guaranteed. The high-pressure low-melting-point brittle porous ceramic texture material prepared through photocuring compounding is simple in design, easy to operate, free of pollution in the preparation process and suitable for large-scale application and popularization.

Description

Technical Field

[0001] The invention belongs to the technical field of porous ceramics, and in particular relates to a photocuring composite preparation of a high-pressure, low-melting-point brittle porous ceramic texture material. Background Art

[0002] The safety and lightweight of on-board hydrogen storage tanks are the two most important issues in modern design. The key component in the hydrogen tank, the safety valve, plays the role of overpressure protection. The safety valve is equipped with a temperature control element, whose material is usually a low-melting-point alloy. The alloy state is plastic and the tensile strength is 20-100MPa. The current safety issue puts higher requirements on the performance of the safety valve. When the ambient temperature reaches 110±5℃, the temperature control element can melt instantly, or when the pressure in the hydrogen storage tank is too high, it can break in time, and the hydrogen storage tank can quickly release pressure to avoid explosions in the tank due to overheating or overpressure.

[0003] The existing temperature control element materials of safety valves have the following defects: first, the existing material preparation method is complicated, not easy to operate, and pollution is easily generated during the preparation process; second, the existing alloy material is in a plastic state, which cannot ensure that the storage system is depressurized in time when it is higher than the working pressure, and it is difficult to play a protective role; third, the existing safety valve cannot integrate overheating protection and overpressure protection, which greatly increases the cost of the storage system; fourth, different safety valves have different working pressures, and the adjustability of the pressure resistance parameters of the temperature control element cannot be ensured.

[0004] Therefore, it is necessary to design a photocurable composite to prepare high-pressure, low-melting-point brittle porous ceramic texture material as a temperature control element to solve the above technical problems. Summary of the invention

[0005] In order to solve the technical problems existing in the above-mentioned prior art, the present invention provides a design of a photocuring composite preparation of a high-pressure, low-melting-point brittle porous ceramic texture material.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite, comprising the following steps:

[0008] (1) Determine the porous ceramic texture parameters and create a 3D model;

[0009] (2) Photocuring

[0010] The 3D model in step (1) is printed, cured by ultraviolet laser, degreased, and sintered by stereolithography technology to obtain a zirconia porous ceramic texture;

[0011] (3) Mixed smelting

[0012] Weigh tin, indium and bismuth metal materials according to mass percentage to prepare a low melting point alloy, melt and filter in a vacuum melting furnace to obtain an alloy solution;

[0013] (4) Brittle porous ceramic texture

[0014] Placing the zirconia porous ceramic texture into a mold, pouring the alloy solution of step (3) into it, and cooling it to obtain a cylindrical alloy ingot;

[0015] (5) Processing alloy ingots

[0016] The cylindrical alloy ingot obtained in step (4) is processed according to the size of the safety valve material.

[0017] The 3D model structure in step (1) is as follows: it comprises 3 layers of thin-walled cylinders and 8 longitudinal beams, wherein the height of the thin-walled cylinders and the longitudinal beams are both 15 mm, the 3 layers of thin-walled cylinders are concentric cylinders and connected by longitudinal beams; the longitudinal beams are evenly distributed, and the angle θ between two adjacent longitudinal beams is 45°, and the thickness T1 is 0.5 mm; the outer diameters of the 3 layers of thin-walled cylinders are respectively 10.5 mm for the outer layer cylinder D1, 7.5 mm for the middle layer cylinder D2, and 4.5 mm for the inner layer cylinder D3; a pore with a height H2 of 2.5 mm is cut out from the outer layer cylinder close to the longitudinal beam, the longitudinal pore spacing H1 is 1 mm, and 32 pores are cut out from the D1 thin-walled cylinder array, as shown in the attached figure. Figure 2 shown.

[0018] The middle layer cylinder is cut out of a hole with a height of H2 close to the longitudinal beam, and the longitudinal pore spacing is H1. D2 thin-walled cylinder array cuts out 32 holes, and a total of 64 holes are cut out. Figure 4 shown.

[0019] In the part of the longitudinal beam close to the outer cylinder and the middle cylinder, cut out the pores with thickness T1 and height H2, and the longitudinal pore interval is H1. 32 pores are cut out of the longitudinal beam, and a total of 64 pores are cut out of the array, as shown in the attached figure. Figure 6 shown.

[0020] On the longitudinal beam, the part close to the outer layer cylinder and the middle layer cylinder, the part of the inner layer cylinder and the middle layer cylinder are cut out, and the pores with thickness T1 and height H2 are cut out. The longitudinal pore interval is H1. 64 pores are cut out of the longitudinal beam array, and a total of 128 pores are cut out. Figure 8 shown.

[0021] The specific steps of step (2) are as follows: printing is performed using XT-C200 ceramic equipment, and UV laser curing is performed simultaneously. After completion, the printing is performed, the printing is performed in a fume hood, and the printing is cleaned using an air gun and a cleaning fluid. After the cleaning is completed, the printing is transferred to a degreasing furnace for debinding for 4 days. After the debinding is completed, the printing is transferred to a sintering furnace for sintering at 1700° C. for 2 days. During the sintering process, the porous ceramic shrinks and becomes dense, thereby obtaining a zirconia porous ceramic texture.

[0022] The specific steps of step (3) are as follows: the mass percentages of tin, indium and bismuth metal materials are 47% tin, 52% indium and 1% bismuth respectively, the low melting point metal materials are proportioned and put into a high frequency vacuum melting furnace, vacuum heated to 350° C., after melting by electromagnetic stirring, the temperature is kept for 20 minutes, the surface slag of the liquid alloy is removed, the temperature is reduced to 200° C., and then filtered by foamed alumina, the melting point range of the formed tin-indium-bismuth alloy is 113.8° C. to 115.2° C.

[0023] The specific steps of step (4) are as follows: placing the zirconia porous ceramic texture in a vertical manner in a mold, pouring the liquid alloy filtered in step (3), using the porous ceramic texture as a brittle fracture skeleton, and after cooling to room temperature, obtaining a cylindrical alloy ingot.

[0024] The specific steps of step (5) are as follows: using an angle grinder and machining equipment to process the cylindrical alloy ingot obtained after cooling according to the shape and size of the safety valve material.

[0025] A method for preparing high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite is disclosed. The porous ceramic texture material prepared is applied to the safety valve of the vehicle-mounted hydrogen storage tank.

[0026] The present invention is not limited to determining the shape, size, pore size, number of pores and arrangement of porous ceramics. First, a 3D model of porous ceramic texture is created; a zirconia porous ceramic texture is obtained by printing, degreasing and sintering through stereoscopic photocuring technology, and finally a tin-indium-bismuth low-melting-point alloy is cast (citing the previous patent of this research group "Design and Preparation Method of Hydrogen Valve High-Pressure Temperature Control Fusing Alloy", patent number CN 117737538A). The process can be used to control the compressive properties of the composite porous ceramic texture material within the low melting point range of 110±5℃. The compressive parameters of the photocuring composite preparation of high-pressure low-melting-point brittle porous ceramic texture materials disclosed in the present invention are adjustable.

[0027] The beneficial effects of the present invention are as follows:

[0028] The compressive performance range of the photocurable composite high-pressure, low-melting-point brittle porous ceramic texture material disclosed in the present application is relatively small. When applied to the safety valve of the on-board hydrogen storage tank, when the pressure in the hydrogen storage tank is too high, the brittle ceramic texture as the skeleton breaks, the valve core moves, and the gas is released to ensure that the hydrogen storage tank does not have an accident under the working pressure; at the same time, the cast low-melting-point tin-indium-bismuth alloy can melt instantly when the ambient temperature rises, and release gas from the gaps in the ceramic texture to ensure safety pressure. The photocurable composite high-pressure, low-melting-point brittle porous ceramic texture material disclosed in the present application is simple in design and easy to operate, and the preparation process is pollution-free, which is suitable for large-scale promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of the principle of the safety valve in the present invention;

[0030] Figure 2 This is a schematic diagram of the overall structure of the brittle porous ceramic texture 3D model in Example 1;

[0031] Figure 3 is the compressive stress-strain diagram of the alloy ingot in Example 1;

[0032] Figure 4 This is a schematic diagram of the overall structure of the brittle porous ceramic texture 3D model in Example 2;

[0033] Figure 5 is the compressive stress-strain diagram of the alloy ingot in Example 2;

[0034] Figure 6 This is a schematic diagram of the overall structure of the brittle porous ceramic texture 3D model in Example 3;

[0035] Figure 7 is the compressive stress-strain diagram of the alloy ingot in Example 3;

[0036] Figure 8 This is a schematic diagram of the overall structure of the brittle porous ceramic texture 3D model in Example 4;

[0037] Fig. 9 This is the compressive stress-strain diagram of the alloy ingot in Example 4. DETAILED DESCRIPTION

[0038] The following content will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention, so that those skilled in the art can fully understand the present invention. Obviously, the described embodiments are only part of the preferred embodiments of the present invention, rather than all the embodiments. Any equivalent transformation or substitution made by ordinary technicians in this field to the following implementation methods without creative work belongs to the protection scope of the present invention.

[0039] The porous ceramic textures of the present invention (a total of four groups as follows) are all composed of 3 layers of thin-walled cylinders and 8 longitudinal beams, the angle θ between the longitudinal beams is 45°, the thickness T1 is 0.5mm, the thickness T2 of the 3 layers of thin-walled cylinders is 0.5mm, the outer diameters D1 are 10.5mm, D2 are 7.5mm, and D3 are 4.5mm. The overall height of the porous ceramic texture is 15mm, and the number and arrangement of its pores are increased on the longitudinal beams and thin-walled cylinders.

[0040] Example 1

[0041] A method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite preparation, comprising the steps of (1) determining Figure 2 The porous ceramic texture parameters are calculated and a 3D model is created; step (2), photo-stereolithography processing; step (3), mixed smelting; step (4), adding brittle porous ceramic texture; step (5), processing alloy ingots; step (6), installing a safety valve.

[0042] In the above step (1), the overall structure of the 3D model is as follows: a hole with a height H2 of 2.5 mm is cut out on the outer cylinder close to the longitudinal beam, the longitudinal pore spacing H1 is 1 mm, and 32 holes are cut out of the D1 thin-walled cylinder array.

[0043] Among them, in the above step (2), the molding process is as follows: printing is performed by XT-C200 ceramic equipment, and UV laser curing is performed at the same time. After completion, the printing is performed, the printing is performed, and the printing is performed in a fume hood and cleaned with an air gun and a cleaning fluid. After the cleaning is completed, the printing is transferred to a degreasing furnace for debinding for 4 days. After the debinding is completed, the printing is transferred to a sintering furnace for sintering at 1700°C for 2 days. During the sintering process, the porous ceramic shrinks and becomes dense, and a porous ceramic texture that meets the final size is obtained.

[0044] In the above step (3), the mass percentages of the raw materials are 47% tin, 52% indium, and 1% bismuth, respectively. The specific steps are: the low melting point metal materials are proportioned and put into a high-frequency vacuum melting furnace, vacuum heated to 350°C, melted by electromagnetic stirring, and kept warm for 20 minutes, the surface slag of the liquid alloy is removed, the temperature is reduced to 200°C, and then filtered using foamed alumina. The melting point range of the tin-indium-bismuth alloy is 113.8°C to 115.2°C.

[0045] In the above step (4), four groups of porous ceramic textures are placed vertically in a mold, and the liquid alloy filtered in step (3) is poured into it. The porous ceramic texture serves as a brittle fracture skeleton. After cooling to room temperature, a cylindrical alloy ingot is obtained.

[0046] In the above step (5), the cylindrical alloy ingot obtained after cooling is processed according to the shape and size of the safety valve material using an angle grinder and machining equipment. After cutting, the alloy ingot has a diameter of 19 mm and a height of 15 mm.

[0047] The alloy ingot was prepared, and the compressive strength of the alloy ingot at brittle fracture was tested by a WDW microcomputer-controlled electronic universal testing machine, and the result was 247 MPa.

[0048] Example 2

[0049] A preparation method for a photocurable composite preparation of a high-pressure, low-melting-point brittle porous ceramic texture material design, the overall structure of the 3D model is: the intermediate layer cylinder is close to the longitudinal beam and a pore with a height of H2 is cut out, and the longitudinal pore spacing is H1, D2. The thin-walled cylinder array cuts out 32 pores, and a total of 64 pores are cut out, as shown in the attached figure. Figure 4 The preparation method is the same as that in Example 1, and the alloy ingot is prepared. The compressive strength at brittle fracture is 35.7 MPa when tested by a WDW microcomputer-controlled electronic universal testing machine.

[0050] Example 3

[0051] A preparation method for a photocurable composite preparation of a high-pressure, low-melting-point brittle porous ceramic texture material design, the overall structure of the 3D model is: the part of the longitudinal beam close to the outer cylinder and the middle cylinder, the pores with a thickness of T1 and a height of H2 are cut off, the longitudinal pore interval is H1, 32 pores are cut off from the longitudinal beam, and a total of 64 pores are cut off from the array, as shown in the attached figure. Figure 6 The preparation method is the same as that of Example 1, and the alloy ingot is prepared. The compressive strength of the alloy ingot at brittle fracture is 175.7 MPa when tested by a WDW microcomputer-controlled electronic universal testing machine.

[0052] Example 4

[0053] A preparation method for a photocurable composite high-pressure, low-melting-point brittle porous ceramic texture material design, the overall structure of the 3D model is: the outer layer cylinder and the middle layer cylinder part, the inner layer cylinder and the middle layer cylinder part are closely attached to the longitudinal beam, the pores with thickness T1 and height H2 are cut off, the longitudinal pore interval is H1, 64 pores are cut off from the longitudinal beam array, and a total of 128 pores are cut off, as shown in the attached figure. Figure 8 The preparation method is the same as that in Example 1, and an alloy ingot (d) is prepared. The compressive strength of the alloy ingot at brittle fracture is 39.7 MPa when tested by a WDW microcomputer-controlled electronic universal testing machine.

[0054] The brittle fracture compressive strength of the alloy ingots of various embodiments is shown in the following table:

[0055]

[0056] Based on the above, the advantages of the present invention are: the present invention utilizes porous ceramic texture to prepare alloy ingots for use in safety valves, and the compressive strength of the alloy ingot can be adjusted between 35.7 and 247 MPa as the number and arrangement of pores in the porous ceramic texture change, which can meet the normal use requirements of safety valves of hydrogen storage tanks with different working pressures. The alloy ingot uses a low melting point alloy with a melting temperature range of 110±5°C and a small melting range. Once the ambient temperature rises, it can melt instantly, and has higher safety performance. At the same time, the preparation method is simple, the process is pollution-free, and it is easy to operate, which is suitable for large-scale promotion and use.

[0057] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the present invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite, characterized in that: The following steps are involved: (1) Determine the porous ceramic texture parameters and create a 3D model; (2) Photocuring The 3D model in step (1) is printed, UV laser cured, degreased, and sintered by stereolithography technology to obtain a zirconia porous ceramic texture; (3) Mixed smelting Weigh tin, indium and bismuth metal materials according to mass percentage to prepare a low melting point alloy, melt and filter in a vacuum melting furnace to obtain an alloy solution; (4) Brittle porous ceramic texture The zirconia porous ceramic texture is placed in a mold, and the alloy solution of step (3) is poured into and cooled to obtain a cylindrical alloy ingot; (5) Processing alloy ingots The cylindrical alloy ingot obtained in step (4) is processed according to the size of the safety valve material.

2. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 1, characterized in that: The 3D model structure in step (1) is as follows: it comprises 3 layers of thin-walled cylinders and 8 longitudinal beams, wherein the height of the thin-walled cylinders and the longitudinal beams are both 15 mm, the 3 layers of thin-walled cylinders are concentric cylinders and are connected by the longitudinal beams; the longitudinal beams are evenly distributed, and the angle θ between two adjacent longitudinal beams is 45°, and the thickness T1 is 0.5 mm; the outer diameters of the 3 layers of thin-walled cylinders are respectively 10.5 mm for the outer layer cylinder D1, 7.5 mm for the middle layer cylinder D2, and 4.5 mm for the inner layer cylinder D3; a pore with a height H2 of 2.5 mm is cut out from the outer layer cylinder close to the longitudinal beam, the longitudinal pore spacing H1 is 1 mm, and 32 pores are cut out of the D1 thin-walled cylinder array.

3. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 2, characterized in that: The middle layer cylinder has holes with a height of H2 cut out close to the longitudinal beam, and the longitudinal pore spacing is H1. D2 thin-walled cylinder array has 32 holes cut out, and a total of 64 holes are cut out.

4. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 2, characterized in that: In the part of the longitudinal beam close to the outer cylinder and the middle cylinder, holes with a thickness of T1 and a height of H2 are cut out, and the longitudinal hole interval is H1. 32 holes are cut out of the longitudinal beam, and a total of 64 holes are cut out of the array.

5. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 3, characterized in that: On the longitudinal beam, the parts close to the outer cylinder and the middle cylinder, the parts of the inner cylinder and the middle cylinder are cut out with pores of thickness T1 and height H2. The longitudinal pore interval is H1. 64 pores are cut out of the longitudinal beam array, and a total of 128 pores are cut out.

6. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 1, characterized in that: The specific steps of step (2) are as follows: printing is performed using XT-C200 ceramic equipment, and UV laser curing is performed at the same time. After completion, the printing is performed, the printing is performed in a fume hood, and the printing is cleaned using an air gun and a cleaning solution. After the cleaning is completed, the printing is transferred to a degreasing furnace for debinding for 4 days. After the debinding is completed, the printing is transferred to a sintering furnace for sintering at 1700° C. for 2 days. During the sintering process, the porous ceramic shrinks and becomes dense, thereby obtaining a zirconia porous ceramic texture.

7. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 1, characterized in that: The specific steps of step (3) are as follows: the mass percentages of tin, indium and bismuth metal materials are 47% tin, 52% indium and 1% bismuth respectively, the low melting point metal materials are proportioned and put into a high frequency vacuum melting furnace, vacuum heated to 350°C, and melted by electromagnetic stirring, and then kept warm for 20 minutes, the surface slag of the liquid alloy is removed, the temperature is reduced to 200°C, and then filtered by foamed alumina, and the melting point range of the formed tin-indium-bismuth alloy is 113.8°C~115.2°C.

8. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 1, characterized in that: The specific steps of step (4) are as follows: placing the zirconia porous ceramic texture in a vertical manner in a mold, pouring the liquid alloy filtered in step (3), using the porous ceramic texture as a brittle fracture skeleton, and after cooling to room temperature, obtaining a cylindrical alloy ingot.

9. The method for preparing a high-pressure, low-melting-point brittle porous ceramic texture material by photocuring composite according to claim 1, characterized in that: The specific steps of step (5) are as follows: Use an angle grinder and machining equipment to process the cylindrical alloy ingot obtained after cooling according to the shape and size of the safety valve material.

10. A porous ceramic textured material prepared by the method for preparing a high-pressure, low-melting-point brittle porous ceramic textured material by photocuring composite as claimed in any one of claims 1 to 9 is applied to a safety valve of an on-vehicle hydrogen storage tank.

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