Ceramic heat insulation paper based on MAX phase material and preparation method thereof
By introducing MAX phase materials and specific preparation processes, porous ceramic heat-insulated paper with high porosity and uniform pore size was prepared, which solved the problem of ceramic heat-insulated paper's performance degradation in humid environments and heat loss at high temperatures, improved mechanical strength and oxidation resistance, and was suitable for extreme high-temperature environments.
Patent Information
- Application Number
- CN202510375352.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-27
- Publication Date
- 2025-07-25
AI Technical Summary
The existing ceramic heat-insulating paper has problems such as degradation in humid environments, insufficient mechanical properties, poor acid and alkali resistance, serious heat loss at high temperatures, and the impact of organic matter combustion, which limits its application in specific environments.
Using the formulation of MAX phase materials and organic solvents, precursors and catalysts, ceramic heat-insulated paper with porous structures is prepared through electrospinning technology, combined with high temperature sintering and nitrogen atmosphere treatment, a porous structure with high poresity and uniform pore size is formed, enhancing mechanical strength and oxidation resistance.
It improves the thermal stability, mechanical strength and oxidation resistance of ceramic heat-insulating paper, reduces thermal conductivity, is suitable for extreme high temperature environments, and broadens the application range, especially in the aerospace field, which has good thermal insulation performance.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of special ceramic materials, and more specifically, relates to a ceramic heat insulation paper based on MAX phase materials and a preparation method thereof. Background Art
[0002] Ceramic heat insulation paper, especially ceramic fiber paper, as an important thermal insulation material, has been widely used in many fields such as construction, medical, electronics, automotive, aerospace, petrochemical, power, and metallurgy. Ceramic heat insulation paper, such as aluminosilicate ceramic fiber paper, exhibits excellent fire resistance, high temperature resistance, heat insulation, insulation, and noise reduction properties. Its temperature resistance range can reach 1260°C to 1400°C, and the thermal conductivity at 800°C can be as low as 0.12 w / (m·k), which makes its application in high-temperature environments possible. In terms of technological innovation, the material properties of ceramic heat insulation paper are constantly being optimized, such as improving high-temperature resistance and heat preservation efficiency. At the same time, the improvement of the production process has also achieved remarkable results in reducing costs and improving production efficiency, but there are still some deficiencies in its research.
[0003] Ceramic heat insulation paper is easily affected in a wet or humid environment. Its fibers have water absorption, and they will become hard after absorbing water, resulting in a significant decrease in heat insulation performance. This is a problem that needs special attention for equipment or pipelines that need to be exposed to a humid environment for a long time. The fiber structure of ceramic heat insulation paper is soft and easily damaged, and it is easy to be cut, scratched, or damaged. This characteristic makes ceramic heat insulation paper perform poorly in occasions where it is subjected to mechanical impact or needs to be frequently deformed (such as wrapping, bending, etc.), restricting its use in certain specific application scenarios and increasing the cost of maintenance and replacement. Ceramic heat insulation paper cannot withstand the erosion of corrosive media such as strong acids and strong alkalis for a long time. In practical applications, special surface treatment or other protective measures may be required for ceramic heat insulation paper, but these additional treatment steps will increase the cost and complexity of the material. Although the thermal conductivity of ceramic heat insulation paper is relatively low, there will still be a certain amount of heat loss at extremely high temperatures. This means that in some occasions with extremely high temperature control requirements, ceramic heat insulation paper may not fully meet the needs. Therefore, when selecting thermal insulation materials, a comprehensive evaluation needs to be carried out according to the specific working environment and temperature requirements. Some ceramic heat insulation papers contain a certain proportion of organic substances (such as sizing agents), and these organic substances may burn and release heat at high temperatures, thus affecting the heat insulation effect. For example, in some applications, the temperature rise caused by the combustion of organic substances may exceed the design requirements.
[0004] MAX phase is a type of ternary layered carbide or nitride material with a special crystal structure, which is composed of metal elements M (such as transition metal elements such as titanium, vanadium, chromium, etc.), main group elements A (such as aluminum, etc.) and carbon or nitrogen elements X. Its basic chemical formula can be expressed as M(n+1)AXn, among which Ti3SiC2 is the most widely studied. MAX phase materials have a series of excellent properties due to their unique nano-layered crystal structure, including high hardness, high toughness, good electrical and thermal conductivity, and excellent oxidation resistance and corrosion resistance. These properties make MAX phase materials have broad application prospects in the fields of high-temperature structural materials, electrode brush materials, chemical anti-corrosion materials and high-temperature heating materials.
[0005] In summary, although the research on ceramic thermal insulation paper has made significant progress, it still has shortcomings in terms of performance stability, mechanical properties, acid and alkali resistance, heat loss at high temperature, and organic matter content under specific environments. Improvements and optimizations should be made to these problems, and by introducing MAX phase materials, ceramic thermal insulation paper with higher strength and corrosion resistance should be developed to broaden its application areas in order to improve the comprehensive performance and application range of ceramic thermal insulation paper. Summary of the invention
[0006] In view of the above problems existing in the prior art, the technical problem to be solved by the present invention is to provide a ceramic thermal insulation paper based on MAX phase materials. Another technical problem to be solved by the present invention is to provide a method for preparing ceramic thermal insulation paper based on MAX phase materials, which is used to prepare ceramic thermal insulation paper with high comprehensive performance and wide application range.
[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
[0008] A ceramic thermal insulation paper based on MAX phase material, the formula of which includes 30-40 wt% MAX phase material, 25-30 wt% organic solvent, 20-25 wt% precursor and 0.3-0.5 wt% catalyst.
[0009] The MAX phase material is selected from one or more of Ti3AlC2, Ti2AlC and Ti2SnC.
[0010] The organic solvent is selected from ethanol or isopropanol.
[0011] The precursor is selected from polycarbosilane or polysilazane.
[0012] The catalyst is selected from nitric acid or hydrochloric acid.
[0013] Ceramic thermal insulation paper based on MAX phase material, the formula includes 40 wt% Ti3AlC2, 30 wt% ethanol, 20 wt% polycarbosilane, and 0.5 wt% hydrochloric acid.
[0014] Ceramic heat-insulating paper based on MAX-phase material, the formula includes 35 wt% Ti2AlC, 25 wt% isopropanol, 25 wt% polysilazane, and 0.3 wt% nitric acid.
[0015] The preparation method of the ceramic heat-insulating paper includes:
[0016] 1) Disperse the MAX-phase material powder in an organic solvent and ensure uniform dispersion through ultrasonic treatment;
[0017] 2) Add a polymer precursor and a catalyst to the dispersion liquid and form a uniform mixed solution through stirring;
[0018] 3) Heat and stir the mixed solution to form a composite sol;
[0019] 4) Prepare a composite fiber membrane from the composite sol through electrospinning technology;
[0020] 5) Perform high-temperature heat treatment on the composite fiber membrane in an inert atmosphere, and finally obtain a ceramic heat-insulating paper with a porous structure through a specific heating and cooling program.
[0021] The inert atmosphere is argon or nitrogen.
[0022] The heating and cooling program is to heat to 1400 °C at a heating rate of 10 °C / min, keep warm for 1 hour, then cool to 800 °C at a cooling rate of 5 °C / min, and then naturally cool to room temperature.
[0023] Compared with the prior art, the beneficial effects of the present invention are:
[0024] 1) The ceramic heat-insulating paper prepared by the present invention has excellent high-temperature performance. The synergistic effect of the MAX-phase material and the polymer precursor enhances the thermal stability and mechanical strength of the material, meeting the requirements of extreme working conditions.
[0025] 2) The present invention significantly improves the high-temperature resistance of the material through high-temperature sintering at 1400 °C in combination with a nitrogen atmosphere, and can be stably used in an extremely high-temperature environment, and is suitable for the high-temperature environment in the aerospace field.
[0026] 3) The present invention performs high-temperature sintering in a nitrogen atmosphere, enhancing the antioxidant performance of the material, making it not easy to oxidize in a high-temperature environment and extending the service life.
[0027] 4) The present invention forms a porous structure with a high porosity (>85%) and a uniform pore size distribution by means of a heating rate of 10 °C / min and controlled-rate cooling (from 5 °C / min to 800 °C), effectively reducing the thermal conductivity (<0.05 W / m·K); the porous structure significantly reduces the material density, meeting the requirements for lightweight thermal insulation materials in the aerospace field.
[0028] 5) By optimizing the sintering process and atmosphere control, the preparation process of the present invention has high controllability and repeatability and is suitable for large-scale production. Detailed implementation manners
[0029] The present invention will be further described below in conjunction with specific embodiments. These embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. Without departing from the spirit and essence of the present invention, any modification or replacement made to the methods, steps or conditions of the present invention shall fall within the scope of the present invention. Unless otherwise specified in the following embodiments, the technical means used in the embodiments are all conventional means well-known to those skilled in the art.
[0030] Example 1
[0031] Disperse 40 wt% of Ti3AlC2 powder in 30 wt% of ethanol, and perform ultrasonic treatment for 30 minutes to ensure uniform dispersion; add 20 wt% of polycarbosilane and 0.5 wt% of hydrochloric acid, and stir magnetically for 2 hours to obtain a mixed solution; place the mixed solution in a water bath at 60 °C and continuously stir for 6 hours to carry out a sol-gel reaction to obtain a MAX phase / polycarbosilane composite sol; load the composite sol into an electrospinning device, set the voltage to 15 kV, the receiving distance to 15 cm, and the spinning speed to 1 mL / h to obtain a MAX phase / polycarbosilane composite fiber membrane; place the composite fiber membrane in a tubular furnace, heat it to 1200 °C at a heating rate of 5 °C / min under an argon atmosphere, keep it warm for 2 hours, and then naturally cool it to room temperature to obtain a ceramic thermal insulation paper with a porous structure.
[0032] Example 2
[0033] In this example, the obtained MAX phase / polycarbosilane composite fiber membrane is placed in a tubular furnace, heated to 1400 °C at a heating rate of 10 °C / min under a nitrogen atmosphere, kept warm for 1 hour, then cooled to 800 °C at a cooling rate of 5 °C / min, and then naturally cooled to room temperature to obtain a ceramic thermal insulation paper with a porous structure. Other steps are the same as those in Example 1.
[0034] Example 3
[0035] In this example, the obtained MAX phase / polycarbosilane composite fiber membrane was placed in a tube furnace and heated to 1300 °C at a heating rate of 8 °C / min under an argon atmosphere, held for 1.5 hours, then cooled to 600 °C at a cooling rate of 3 °C / min, and further cooled to room temperature naturally to obtain a ceramic thermal insulation paper with a porous structure. Other steps were the same as those in Example 1.
[0036] Example 4
[0037] In this example, the obtained MAX phase / polycarbosilane composite fiber membrane was placed in a tube furnace and heated to 1000 °C at a heating rate of 10 °C / min under an argon atmosphere, held for 1 hour, then cooled to room temperature at a cooling rate of 5 °C / min to obtain a ceramic thermal insulation paper with a porous structure. Other steps were the same as those in Example 1.
[0038] As shown in Table 1, the product prepared in Example 2 showed the best performance. Its low collapse rate (2.5%), low thermal conductivity (0.028 W / (m·K)), and high service temperature (≤1600 °C) made it the first choice for high-performance, high-temperature application scenarios.
[0039] Table 1 Performance comparison of ceramic thermal insulation papers prepared at different heating rates
[0040]
[0041] Example 5
[0042] 35 wt% of Ti2AlC powder was dispersed in 25 wt% of isopropanol and ultrasonically treated for 30 minutes to ensure uniform dispersion; 25 wt% of polysilazane and 0.3 wt% of nitric acid were added and magnetically stirred for 2 hours to obtain a mixed solution; the mixed solution was placed in a water bath at 70 °C and continuously stirred for 5 hours to obtain a MAX phase / polysilazane composite sol; the composite sol was loaded into an electrospinning device, with the voltage set at 18 kV, the receiving distance at 20 cm, and the spinning speed at 0.8 mL / h to obtain a MAX phase / polysilazane composite fiber membrane; the composite fiber membrane was placed in a tube furnace and heated to 1400 °C at a heating rate of 10 °C / min under a nitrogen atmosphere, held for 1 hour, then cooled to 800 °C at a cooling rate of 5 °C / min, and further cooled to room temperature naturally to obtain a ceramic thermal insulation paper with a porous structure.
[0043] Example 6
[0044] Disperse 30 wt% Ti2SnC powder in 25 wt% isopropanol and ultrasonically treat it for 30 minutes to ensure uniform dispersion; add 25 wt% polysilazane and 0.3 wt% nitric acid, and stir magnetically for 2 hours to obtain a mixed solution; place the mixed solution in a water bath at 70 °C and continuously stir for 5 hours to obtain a MAX phase / polysilazane composite sol; load the composite sol into an electrospinning device, set the voltage to 18 kV, the receiving distance to 20 cm, and the spinning speed to 0.8 mL / h to obtain a MAX phase / polysilazane composite fiber membrane; place the composite fiber membrane in a tube furnace, heat it to 1400 °C at a heating rate of 10 °C / min under a nitrogen atmosphere, hold for 1 hour, then cool it to 800 °C at a cooling rate of 5 °C / min, and then naturally cool it to room temperature to obtain a ceramic thermal insulation paper with a porous structure.
[0045] As shown in Table 2, the Ti3AlC2 system exhibits the best performance in terms of mechanical strength and thermal conductivity, the Ti2AlC system has advantages in thermal insulation performance and porosity, while the Ti2SnC system is more prominent in chemical stability.
[0046] Table 2 Performance comparison of ceramic thermal insulation papers prepared from different MAX phase materials
[0047]
[0048] Example 7
[0049] Disperse 20 wt% Ti(OC4H9)4 and 10 wt% aluminum isopropoxide in 50 wt% deionized water and stir magnetically for 2 hours to form a uniform mixed solution; add 5 wt% graphene oxide and continue to stir for 1 hour to ensure uniform dispersion of graphene oxide; add 15 wt% polyvinyl alcohol, heat and stir in a water bath at 80 °C for 4 hours to form a viscous precursor sol; transfer the precursor sol to a high-pressure reaction kettle and carry out a hydrothermal reaction at 180 °C for 12 hours; after the reaction, cool it to room temperature to obtain a hydrothermally synthesized composite gel; place the composite gel in a freeze dryer, freeze it at -50 °C for 24 hours, and then dry it under vacuum conditions for 48 hours to obtain a preformed material with a porous structure; place the preformed material in a tube furnace, heat it to 1600 °C at a heating rate of 5 °C / min under an argon atmosphere, hold for 2 hours; then cool it to 1000 °C at a cooling rate of 3 °C / min, and then naturally cool it to room temperature to obtain a ceramic thermal insulation material with a porous structure.
[0050] Example 8
[0051] Add 40 wt% aluminosilicate fiber to 40 wt% deionized water and stir at high speed for 2 hours to form a uniform fiber dispersion; add 5 wt% carboxymethyl cellulose (CMC) and continue stirring for 1 hour to ensure that the CMC is fully dissolved and uniformly mixed with the fiber; add 10 wt% polyvinyl alcohol (PVA) to the fiber dispersion, heat and stir in an 80 °C water bath for 4 hours to form a viscous slurry; add 5 wt% polystyrene microspheres as pore formers and continue stirring for 30 minutes to ensure that the microspheres are uniformly dispersed; pour the slurry into a forming mold and use a vacuum filtration device to remove excess water to form a wet fiber paper; place the wet fiber paper in a flattening machine and flatten it at a pressure of 0.5 MPa for 1 minute to obtain a uniform preformed paper. Place the preformed paper in a drying oven and dry it at 80 °C for 12 hours to remove residual moisture; place the dried paper in a tube furnace and heat it to 600 °C at a heating rate of 5 °C / min in an air atmosphere and hold for 2 hours to completely decompose the organic binder to obtain a ceramic thermal insulation paper with a porous structure.
[0052] The results are shown in Table 3. The product prepared in Example 7 showed the best performance in terms of tensile strength, elastic modulus, and tear strength due to the strengthening effect of graphene. However, the addition of graphene increased the cost, had a relatively high thermal conductivity (0.08 W / (m·K)), the worst oxidation resistance, was easily oxidized at high temperatures, and had the highest collapse rate, making it unsuitable for fields with extremely high requirements for thermal insulation performance; the product prepared in Example 2 had excellent mechanical properties, was suitable for high-performance thermal insulation fields, had a thermal conductivity as low as 0.035 W / (m·K), a moderate density (250 kg / m 3 ), a high-temperature resistance of 1600 °C, and was suitable for high-requirement scenarios such as aerospace and industrial furnace thermal insulation; the product prepared in Example 8 had relatively low mechanical properties and good flexibility, but had a low cost and was suitable for building insulation and low-temperature thermal insulation, etc.
[0053] Table 3 Performance comparison of ceramic thermal insulation papers prepared by different preparation methods
[0054]
[0055] In summary, the product prepared in Example 2 had a high porosity and a uniform pore size distribution and was suitable for the aerospace field; the product prepared in Example 5 had slightly worse performance than that in Example 2 and was suitable for high-temperature thermal insulation scenarios. The porosities of the other examples were relatively low or the distributions were uneven, and their applicable scenarios were limited.
[0056] The above description is illustrative rather than restrictive to the present invention. Those of ordinary skill in the art understand that many modifications, variations, or equivalents can be made without departing from the spirit and scope defined by the appended claims, and all of them will fall within the protection scope of the present invention.
Claims
1. A ceramic heat-insulating paper based on MAX-phase material, characterized in that, The formulation comprises 30 - 40 wt% MAX phase material, 25 - 30 wt% organic solvent, 20 - 25 wt% precursor, and 0.3 - 0.5 wt% catalyst.
2. The ceramic heat-insulating paper according to claim 1, characterized in that The MAX phase material is selected from one or more of Ti3AlC2, Ti2AlC, and Ti2SnC.
3. The ceramic heat-insulating paper according to claim 1, wherein The organic solvent is selected from ethanol or isopropyl alcohol.
4. The ceramic heat-insulating paper according to claim 1, wherein The precursor is selected from polycarbosilane or polysilazane.
5. The ceramic heat-insulating paper according to claim 1, characterized in that, The catalyst is selected from nitric acid or hydrochloric acid.
6. The ceramic heat insulation paper according to claim 1, characterized in that The formulation comprises 40 wt% Ti3AlC2, 30 wt% ethanol, 20 wt% polycarbosilane, and 0.5 wt% hydrochloric acid.
7. The ceramic heat insulation paper according to claim 1, characterized in that The formulation comprises 35 wt% Ti2AlC, 25 wt% isopropyl alcohol, 25 wt% polysilazane, and 0.3 wt% nitric acid.
8. The preparation method of the ceramic heat insulation paper according to any one of claims 1-7, characterized in that, It includes: 1) Disperse the MAX phase material powder in the organic solvent and ensure uniform dispersion through ultrasonic treatment; 2) Add the polymer precursor and the catalyst to the dispersion and form a uniform mixed solution through stirring; 3) Heat and stir the mixed solution to form a composite sol; 4) Prepare a composite fiber membrane from the composite sol through electrospinning technology; 5) Conduct high-temperature heat treatment on the composite fiber membrane in an inert atmosphere and finally obtain a ceramic thermal insulation paper with a porous structure through a specific heating and cooling program.
9. The preparation method according to claim 8, characterized in that, The inert atmosphere is argon or nitrogen.
10. The preparation method according to claim 8, characterized in that, The heating and cooling program is to heat to 1400 °C at a heating rate of 10 °C / min, hold for 1 hour, then cool to 800 °C at a cooling rate of 5 °C / min, and then cool naturally to room temperature.