Preparation method of high-strength glass sealing material for high-pressure liquid heater

Abstract

The invention discloses a preparation method of a high-strength glass sealing material for a high-pressure liquid heater, and relates to the technical field of preparation of glass sealing materials. The invention relates to a preparation method of a high-strength glass sealing material for a high-pressure liquid heater. The preparation method comprises the following steps: respectively weighing CaO, Al2O3, B2O3 and SiO2 according to the formula proportion of each raw material, and uniformly mixing; putting the uniformly mixed raw materials into a crucible, and smelting at 1350-1450 DEG C to prepare a glass matrix; taking out the glass matrix from the crucible and carrying out water quenching; carrying out ball milling on the water-quenched glass matrix to obtain first glass powder; adding zirconium oxide fibers into the obtained first glass powder, and fully mixing to obtain second glass powder; according to the high-strength glass sealing material developed by the invention, the temperature resistance, the shear strength and the sealing performance of the glass sealing material are remarkably improved by optimizing a glass formula and redesigning a glass preparation process.

Description

Technical Field

[0001] The present invention relates to the technical field of glass sealing material preparation, and specifically relates to a method for preparing a high-strength glass sealing material for a high-pressure liquid heater. Background Art

[0002] A high-pressure liquid heater is a key component in the thermal management system of a new energy vehicle's power battery. The function of the high-pressure liquid heater is to ensure the stable performance of the power battery under extremely cold conditions and slow down the decline of battery performance.

[0003] The high-pressure liquid heater consists of two parts: a heating element and a water circulation component, and relies on a glass sealing material to seal the two. The glass sealing material is one of the key components and development difficulties of the high-pressure liquid heater.

[0004] Figure 1 As shown; the glass sealing material is between the water circulation component and the positive and negative electrode points. Its function is to achieve a reliable seal between the water circulation component and the heating element, isolate the liquid from the positive and negative electrode points, and ensure safety and no leakage during high-voltage use.

[0005] Regarding the glass sealing material used for sealing between the water circulation component and the heating element in a high-pressure liquid heater, the inventor has found through long-term practical research that the following technical problems will occur during the use of the glass sealing material:

[0006] (1) When the coolant in the high-pressure liquid heater is missing, the heating element will dry burn, and the local surface temperature will quickly exceed 800 °C. The softening temperature of ordinary glass sealing materials is below 650 °C. When the use temperature exceeds 650 °C, the glass softens, and as the temperature continues to rise, the glass gradually crystallizes, forming holes and thermal stress defects, resulting in an increase in air holes in the sealing structure and ultimately leading to sealing failure at high temperatures.

[0007] (2) There is a pressure of 0.3 MPa during the water inlet and outlet process of the water circulation component of the high-pressure liquid heater. When in use, ordinary glass sealing materials need to bear shear stress for a long time, and the shear strength of ordinary glass sealing materials cannot meet the requirements.

[0008] (3) Under normal use conditions, the air leakage rate at the sealing part of the high-pressure liquid heater should be lower than 0.04 sccm / cm (the detection method is helium leak detection); although the leakage amount of ordinary glass sealing materials meets the standard, further optimization is needed.

[0009] Therefore, how to solve the above technical problems and design a glass sealing material with better temperature resistance, shear strength, and sealing performance is the technical problem faced by ordinary technicians in the current field.

[0010] The information disclosed in this background section is only intended to enhance the general understanding of the background of the present invention and should not be regarded as an admission or any form of implication that this information constitutes prior art already known to those of ordinary skill in the art. Summary of the Invention

[0011] In view of the above technical problems, an embodiment of the present invention provides a method for preparing a high-strength glass sealing material for a high-pressure liquid heater to solve the problems raised in the above background art.

[0012] I. The design idea of the present invention is as follows:

[0013] By optimizing the glass formula and redesigning the glass preparation process, zirconia fibers are added after the formation of the glass network structure, with the zirconia fibers being independent of the glass network structure, ensuring that the zirconia fibers are in an independent fibrous structure during the glass preparation process and do not react with other compound raw materials during the glass sintering process;

[0014] For the high-strength glass sealing material prepared by the present invention, the zirconia fibers in the glass sealing material accumulate to form a three-dimensional skeleton structure, which significantly improves the temperature resistance, shear strength, and sealing performance of the glass sealing material;

[0015] In a high-temperature environment, the ordinary glass phase in the high-strength glass sealing material will soften, but the three-dimensional skeleton of zirconia fibers in the high-strength glass sealing material can still effectively support the structure of the ordinary glass phase, significantly improving the temperature resistance and shear strength of the high-strength glass sealing material;

[0016] At the same time, the three-dimensional skeleton of zirconia fibers can also provide a structural support for the high-strength glass sealing material at high temperatures, reducing the deformation amount of the high-strength glass sealing material in a high-temperature environment, preventing the generation and diffusion of microcracks inside the high-strength glass sealing material, and thus improving the sealing performance of the high-strength glass sealing material at high temperatures.

[0017] II. A method for preparing a high-strength glass sealing material for a high-pressure liquid heater includes the following steps:

[0018] Weigh CaO, Al 2 O 3 , B 2 O 3 and SiO 2 respectively according to the formula ratio of each raw material and mix them evenly;

[0019] Put the evenly mixed raw materials in a crucible and carry out melting at 1350°C - 1450°C to prepare a glass matrix;

[0020] Take out the glass matrix from the crucible and perform water quenching; the glass after water quenching will generate large thermal stress inside due to rapid cooling, resulting in the glass becoming harder and having better crack resistance;

[0021] Ball mill the water-quenched glass matrix to obtain the first glass powder; the particle size of the glass powder after ball milling is uniform, increasing the specific surface area of the glass powder, which is helpful for subsequent mixing with zirconia fibers;

[0022] Add zirconia fibers to the obtained first glass powder and mix well to obtain the second glass powder; zirconia fibers can form a three-dimensional skeleton strengthening structure in the glass matrix, enhancing the stability of the material under high temperature and high pressure. It can also improve the thermal conductivity of the glass material, increasing its high-temperature resistance and crack resistance;

[0023] Pour the second glass powder into a molding die and perform dry pressing to form a glass sealing material with a certain shape; the specific shape of the glass sealing material is not limited here, and it is specifically designed according to the shape required by different actual high-pressure liquid heaters;

[0024] Pre-sinter the formed glass sealing material at 650°C - 750°C to make the glass sealing material have a certain structural strength; pre-sintering is to prepare for subsequent high-temperature encapsulation to prevent the glass from deforming during the encapsulation process;

[0025] Assemble the heating element on the high-pressure liquid heater and the glass sealing material; place the assembled heating element and glass sealing material into the furnace and raise the temperature to 1150°C - 1250°C for high-temperature encapsulation; the process of high-temperature encapsulation completely melts and solidifies the glass material to form a strong sealing structure;

[0026] After the high-temperature encapsulation is completed, cool it to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0027] Preferably, by mass, it includes raw materials in the following proportions: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts, and 20 - 50 parts of zirconia fibers.

[0028] Preferably, 35 parts of zirconia fibers.

[0029] Preferably, in the step of ball milling the water-quenched glass matrix to obtain the first glass powder, after the ball milling operation of the glass matrix, it is necessary to screen the first glass powder to screen out the glass powder with uniform particle size.

[0030] Preferably, in the step of melting to prepare the glass matrix at 1350°C - 1450°C, the melting temperature is 1400°C.

[0031] Preferably, in the step of pre-sintering the formed glass sealing material at 650°C - 750°C, the pre-sintering temperature is 700°C

[0032] Preferably, in the step of placing the assembled heating element and the glass sealing material into the furnace chamber and heating up to 1150°C - 1250°C for high-temperature encapsulation, the high-temperature encapsulation temperature is 1200°C.

[0033] The method for preparing a high-strength glass sealing material for a high-pressure liquid heater provided by an embodiment of the present invention has the following beneficial effects: The high-strength glass sealing material developed by the present invention significantly improves the temperature resistance, shear strength, and sealing performance of the glass sealing material by optimizing the glass formula and redesigning the glass preparation process. Description of the Drawings

[0034] Figure 1 It is a schematic structural diagram of a high-pressure liquid heater;

[0035] Figure 2 It is a process flow chart of the method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to the present invention. Detailed Embodiments

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present invention.

[0037] In view of the above technical problems, an embodiment of the present invention provides a method for preparing a high-strength glass sealing material for a high-pressure liquid heater to solve the problems raised in the above background technology.

[0038] I. Experimental Grouping and Product Preparation

[0039] Example 1:

[0040] By mass of the raw materials, the following proportions of raw materials are weighed respectively: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts, and 20 parts of zirconia fiber;

[0041] After weighing the raw materials, first, CaO and Al2 O 3 , B 2 O 3 and SiO 2 Mix well;

[0042] The uniformly mixed raw materials are placed in a crucible and melted at 1400° C. to prepare a glass matrix;

[0043] The glass substrate is removed from the crucible and water quenched;

[0044] Ball-milling the water-quenched glass matrix to obtain a first glass powder;

[0045] Adding zirconium oxide fiber to the obtained first glass powder and mixing thoroughly to obtain a second glass powder;

[0046] Pour the second glass powder into a forming mold for dry pressing to form a glass sealing material of a certain shape;

[0047] Pre-sintering the formed glass sealing material at 700°C to give the glass sealing material a certain structural strength;

[0048] Assembling the heating element and the glass sealing material on the high-pressure liquid heater; placing the assembled heating element and the glass sealing material into the furnace and heating them to 1200°C for high-temperature packaging;

[0049] After high-temperature packaging is completed, cooling is performed to obtain a high-strength glass sealing material assembled on a high-pressure liquid heater.

[0050] Embodiment 2:

[0051] According to the mass percentage of raw materials, weigh the following raw materials respectively: CaO 13 parts, Al 2 O 3 24 copies, B 2 O 3 33 parts, SiO 2 30 parts and 30 parts of zirconium oxide fiber;

[0052] After weighing the raw materials, firstly, CaO, Al 2 O 3 , B 2 O 3 and SiO 2 Mix well;

[0053] The uniformly mixed raw materials are placed in a crucible and melted at 1400° C. to prepare a glass matrix;

[0054] The glass substrate is removed from the crucible and water quenched;

[0055] The water-quenched glass matrix is ball-milled to obtain the first glass powder;

[0056] Zirconia fibers are added to the obtained first glass powder and mixed thoroughly to obtain the second glass powder;

[0057] The second glass powder is poured into a molding die and dry-pressed to form a glass sealing material of a certain shape;

[0058] The formed glass sealing material is pre-sintered at 700 °C to endow the glass sealing material with a certain structural strength;

[0059] The heating element on the high-pressure liquid heater and the glass sealing material are assembled; the assembled heating element and glass sealing material are placed in a furnace and heated to 1200 °C for high-temperature encapsulation;

[0060] After the high-temperature encapsulation is completed, it is cooled to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0061] Example 3:

[0062] By mass of the raw materials, the following proportions of raw materials are weighed respectively: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts and 35 parts of zirconia fibers;

[0063] After the raw materials are weighed, first, CaO, Al 2 O 3 , B 2 O 3 and SiO 2 are mixed evenly;

[0064] The evenly mixed raw materials are placed in a crucible and melted at 1400 °C to prepare a glass matrix;

[0065] The glass matrix is taken out of the crucible and water-quenched;

[0066] The water-quenched glass matrix is ball-milled to obtain the first glass powder;

[0067] Zirconia fibers are added to the obtained first glass powder and mixed thoroughly to obtain the second glass powder;

[0068] The second glass powder is poured into a molding die and dry-pressed to form a glass sealing material of a certain shape;

[0069] The formed glass sealing material is pre-sintered at 700 °C to endow the glass sealing material with a certain structural strength;

[0070] Assemble the heating element and the glass sealing material on the high-pressure liquid heater; place the assembled heating element and glass sealing material into the furnace and raise the temperature to 1200 °C for high-temperature encapsulation;

[0071] After the high-temperature encapsulation is completed, cool it to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0072] Example 4:

[0073] Weigh the following raw materials according to the mass parts: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts, and 40 parts of zirconia fiber;

[0074] After weighing the raw materials, first mix CaO, Al 2 O 3 , B 2 O 3 and SiO 2 evenly;

[0075] Put the evenly mixed raw materials into a crucible and melt them at 1400 °C to prepare a glass matrix;

[0076] Take out the glass matrix from the crucible and perform water quenching;

[0077] Ball-mill the water-quenched glass matrix to obtain the first glass powder;

[0078] Add zirconia fiber to the obtained first glass powder and mix well to obtain the second glass powder;

[0079] Pour the second glass powder into a molding die and perform dry pressing to form a glass sealing material with a certain shape;

[0080] Pre-sinter the formed glass sealing material at 700 °C to make the glass sealing material have a certain structural strength;

[0081] Assemble the heating element and the glass sealing material on the high-pressure liquid heater; place the assembled heating element and glass sealing material into the furnace and raise the temperature to 1200 °C for high-temperature encapsulation;

[0082] After the high-temperature encapsulation is completed, cool it to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0083] Example 5:

[0084] By mass parts of raw materials, weigh the following proportions of raw materials respectively: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts and 50 parts of zirconia fiber;

[0085] After weighing the raw materials, first mix CaO, Al 2 O 3 , B 2 O 3 and SiO 2 uniformly;

[0086] Put the uniformly mixed raw materials in a crucible and melt them at 1400 °C to prepare a glass matrix;

[0087] Take out the glass matrix from the crucible and perform water quenching;

[0088] Ball mill the water-quenched glass matrix to obtain the first glass powder;

[0089] Add zirconia fiber to the obtained first glass powder and mix well to obtain the second glass powder;

[0090] Pour the second glass powder into a molding die and perform dry pressing to form a glass sealing material with a certain shape;

[0091] Pre-sinter the formed glass sealing material at 700 °C to make the glass sealing material have a certain structural strength;

[0092] Assemble the heating element on the high-pressure liquid heater and the glass sealing material; put the assembled heating element and glass sealing material into the furnace chamber and heat up to 1200 °C for high-temperature encapsulation;

[0093] After the high-temperature encapsulation is completed, cool it to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0094] Comparative Example 1:

[0095] By mass parts of raw materials, weigh the following proportions of raw materials respectively: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts;

[0096] After weighing the raw materials, first mix CaO, Al 2 O 3 , B 2 O 3and SiO 2 Mix evenly;

[0097] Put the evenly mixed raw materials in a crucible and melt them at 1400 °C to prepare a glass matrix;

[0098] Take out the glass matrix from the crucible and perform water quenching;

[0099] Ball mill the water-quenched glass matrix to obtain the first glass powder;

[0100] Pour the first glass powder into a molding die and perform dry pressing to form a glass sealing material with a certain shape;

[0101] Pre-sinter the formed glass sealing material at 700 °C to make the glass sealing material have a certain structural strength;

[0102] Assemble the heating element on the high-pressure liquid heater and the glass sealing material; put the assembled heating element and glass sealing material into the furnace chamber and raise the temperature to 1200 °C for high-temperature encapsulation;

[0103] After the high-temperature encapsulation is completed, cool it to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0104] Comparative Example 2:

[0105] By mass of the raw materials, weigh the following proportions of raw materials: 13 parts of CaO, Al 2 O 3 24 parts, B 2 O 3 33 parts, SiO 2 30 parts and 35 parts of zirconia powder;

[0106] After weighing the raw materials, first mix CaO, Al 2 O 3 , B 2 O 3 , SiO 2 35 parts of zirconia powder evenly;

[0107] Put the evenly mixed raw materials in a crucible and melt them at 1400 °C to prepare a glass matrix;

[0108] Take out the glass matrix from the crucible and perform water quenching;

[0109] Ball mill the water-quenched glass matrix to obtain the first glass powder;

[0110] Pour the first glass powder into a molding die and perform dry pressing to form a glass sealing material with a certain shape;

[0111] Pre-sinter the formed glass sealing material at 700 °C to endow the glass sealing material with certain structural strength;

[0112] Assemble the heating element on the high-pressure liquid heater and the glass sealing material; place the assembled heating element and glass sealing material into the furnace and raise the temperature to 1200 °C for high-temperature encapsulation;

[0113] After the high-temperature encapsulation is completed, cool it to obtain a high-strength glass sealing material assembled on the high-pressure liquid heater.

[0114] II. Product performance test

[0115] The product performance test data of Examples 1 - 5 are shown in Table 1 below: From the data results in Table 1, it can be seen that the glass sealing material prepared by the present invention has a high softening temperature, good sealing performance and good shear strength.

[0116] The softening temperature of common ordinary glass sealing materials is below 650 °C, and the softening temperature of the glass sealing material prepared by the present invention is significantly higher than 650 °C; the leakage rate of common ordinary glass sealing materials should be lower than 0.04 sccm / cm, and the leakage rate of the glass sealing material prepared by the present invention is significantly lower than 0.04 sccm / cm; at the same time, the shear strength of the glass sealing material prepared by the present invention is significantly higher than 3 MPa.

[0117] Through further data analysis, it can be known that when the addition amount of zirconia fiber is insufficient, the three-dimensional skeleton structure of zirconia fiber is incomplete and the heat resistance performance is poor; the more the addition amount of zirconia fiber, the better the heat resistance performance, but when it exceeds 35 parts, both the shear strength and the sealing performance decrease significantly; through experiments, it is obtained that when the addition amount of zirconia fiber is 35 parts, a new type of high-strength glass sealing material with optimal performance can be obtained.

[0118] Table 1

[0119]

[0120] The product performance test data of Comparative Example 1 - Comparative Example 2 and Example 3 are shown in Table 2 below: From the data results in Table 2, it can be seen that the zirconia incorporated in the common high-strength glass sealing material prepared in Comparative Example 2 is in a fine powder form, which participates in the network structure of the glass itself and has no improvement effect on the strength and heat resistance performance of the glass. The high-strength glass sealing material prepared in Example 3 of the present invention has significantly better heat resistance performance, shear strength and sealing performance than Comparative Example 1 and Comparative Example 2.

[0121] Table 2

[0122]

[0123] The embodiments described above are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing a high-strength glass sealing material for a high-pressure liquid heater, characterized in that: The following steps are involved: Weigh CaO, Al2O3, B2O3 and SiO2 according to the formula ratio of each raw material and mix them evenly; Putting the uniformly mixed raw materials into a crucible, and melting them at 1350°C-1450°C to prepare a glass matrix; The glass substrate is removed from the crucible and water quenched; Ball-milling the water-quenched glass matrix to obtain a first glass powder; Adding zirconium oxide fiber to the obtained first glass powder and mixing thoroughly to obtain a second glass powder; Pour the second glass powder into a forming mold for dry pressing to form a glass sealing material of a certain shape; Pre-sintering the formed glass sealing material at 650℃-750℃ to give the glass sealing material a certain structural strength; Assemble the heating element and the glass sealing material on the high-pressure liquid heater; put the assembled heating element and the glass sealing material into the furnace and heat them to 1150°C-1250°C for high-temperature packaging. After high-temperature packaging is completed, cooling is performed to obtain a high-strength glass sealing material assembled on a high-pressure liquid heater.

2. The method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to claim 1, characterized in that: The raw materials are included in the following proportions by mass: 13 parts of CaO, 24 parts of Al2O3, 33 parts of B2O3, 30 parts of SiO2 and 20-50 parts of zirconia fibers.

3. The method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to claim 2, characterized in that: 35 parts of zirconia fiber.

4. The method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to claim 1, characterized in that: In the step of ball-milling the water-quenched glass matrix to obtain the first glass powder, the first glass powder needs to be screened after the ball-milling operation of the glass matrix is ​​completed, so as to screen out glass powder with uniform particle size.

5. The method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to claim 1, characterized in that: In the step of preparing the glass matrix by melting at 1350°C-1450°C, the melting temperature is 1400°C.

6. The method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to claim 1, characterized in that: In the step of pre-sintering the formed glass sealing material at 650°C-750°C, the pre-sintering temperature is 700°C.

7. The method for preparing a high-strength glass sealing material for a high-pressure liquid heater according to claim 1, characterized in that: In the step of placing the assembled heating element and glass sealing material into a furnace and heating the furnace to 1150°C-1250°C for high temperature packaging, the temperature of the high temperature packaging is 1200°C.

Images