CN115368163A - Ultra-light medium-entropy carbide ultra-high temperature heat insulation material and preparation method thereof - Google Patents
Ultra-light medium-entropy carbide ultra-high temperature heat insulation material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of ultra-high temperature super heat-insulating materials, in particular to an ultra-light medium-entropy carbide ultra-high temperature heat-insulating material and a preparation method thereof. The carbide has the chemical formula of (Ti) in terms of molar ratio x Zr y Nb 1‑x‑y ) C, wherein: 0<x<1，0<y<1, and x + y<1; porous (Ti) x Zr y Nb 1‑x‑y ) The density of C is 0.25-0.95 g/cm 3 The porosity is 85-96%, and the highest temperature resistance is higher than 2000 ℃. Firstly, titanium carbide, zirconium carbide and niobium carbide powder are used as raw materials to prepare evenly mixed slurry, then foaming, injection molding, freezing and vacuum drying are carried out, and finally high-temperature sintering is carried out, so that the titanium-zirconium-niobium ternary medium entropy carbide ultra-high temperature heat insulation material with ultrahigh porosity and ultra-light weight is prepared. The material has the advantages of ultra-low density, high strength,The material has the characteristics of low thermal conductivity and ultrahigh temperature resistance, and has wide application prospect in the field of aerospace ultrahigh temperature heat insulation. The method has low cost and simple operation, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of ultra-high temperature heat insulation materials, in particular toUltra-light (0.25-0.95 g/cm) 3 ) And resistance to ultra-high temperatures (>2000 ℃ of titanium-zirconium-niobium ternary medium entropy carbide porous ceramic heat insulation material and a preparation method thereof.
Background
The hypersonic aircraft becomes one of the research focuses of countries in the world by virtue of excellent rapid response capability, strong remote attack capability and excellent self-survival capability, and plays an important role in the field of aerospace. With the higher and faster flight speed (> 10 Ma), the aircraft surface temperature reaches above 2000 ℃. Traditional insulation materials, such as: the maximum temperature bearing of the oxide fiber heat insulation tile (alumina, mullite, silica and the like) is lower than 1600 ℃, and the requirement of ultra-high temperature service is difficult to meet, so that the development of a novel ultra-high temperature resistant heat insulation material is urgently needed.
The ultra-high temperature ceramics have very high melting points (>3000 ℃), particularly comprising carbides, borides and nitrides of transition metals, has the advantages of high strength, ultrahigh temperature resistance, ablation resistance and phase stability, and can keep the structural appearance of an aircraft complete and stable for a long time at ultrahigh temperature (W.G.Fahrenholtz, et al, scr.Mater. (materials bulletin). 2016 (129): 94-99)), so that the ultrahigh-temperature ceramic is considered as a novel matrix material with the best ultrahigh-temperature thermal protection. But the general density of the ultra-high temperature ceramics is large (7.79 to 14.50 g/cm) 3 ) And high thermal conductivity (22-33W/(m.K)), and does not meet the requirements of light-weight heat-insulating members. Effective measures must therefore be taken to reduce their density and thermal conductivity. The development of the porous ultrahigh-temperature ceramic with high porosity can obviously reduce the density of the ceramic, simultaneously reduce the solid heat conduction and obtain the heat-insulating material with lower heat conductivity.
According to the current development, although the density and thermal conductivity of the porous ultra-high temperature ceramic are significantly reduced, the actual requirements of weight reduction of components and super thermal insulation are still not met. For example, zrB at 71% porosity 2 The density of the/SiC porous ceramic is 1.70g/cm 3 90% porosity (Hf) 1/3 Ta 1/3 Nb 1/3 ) The density of the C porous ceramic is 1.17g/cm 3 (WU, et al, materialia (journal of materials) 2021 (18): 101158); these materials far exceed American space thermal insulation tile 0.13E0.35g/cm 3 The density of (c). The main reasons for these problems are: the porosity of the material is low (less than or equal to 90 percent) or the density of the matrix material is high ((Hf) 1/3 Ta 1/3 Nb 1/3 ) The theoretical density of C is 11.71g/cm 3 )。
In order to solve the problems, the invention selects titanium carbide with lower density (4.91 g/cm of titanium carbide) 3 6.59g/cm zirconium carbide 3 7.79g/cm of niobium carbide 3 ) The ultra-high temperature ceramic is used as a substrate, the intrinsic thermal conductivity of a framework material is obviously reduced by means of a multi-principal-element solid solution mechanism, and the density of the ultra-high temperature ceramic is obviously reduced by preparing a material with ultra-high porosity (the highest 96%), so that ultra-light weight (the lowest density is about 0.25 g/cm) 3 ) And a medium-entropy carbide ultra-high temperature super heat-insulating material with low thermal conductivity (about 0.15W/(m.K) at the lowest).
In summary, in order to obtain the lightweight ultra-high temperature heat insulating material, titanium carbide and zirconium carbide with lower density and niobium carbide with lowest heat conductivity in the carbide ultra-high temperature ceramic are preferably used as raw materials, and the heat conductivity of the material is reduced by multi-principal element solid solution. The foaming-injection-freezing-drying process is adopted to realize the ultrahigh porosity (> 90%), the sintering aid is added to promote the sintering of the ultrahigh-temperature ceramic and the uniform solid solution of multi-principal-element transition metal elements, and finally the lightweight ultrahigh-temperature heat-insulating material with ultrahigh temperature resistance, ablation resistance, low heat conductivity and high strength is obtained.
Disclosure of Invention
In order to overcome the performance defects (high density and high thermal conductivity) of the existing material system and the defects of the preparation technology, the invention aims to provide an ultra-light medium-entropy carbide ultra-high temperature heat-insulating material and a preparation method thereof, solve the problem that the temperature bearing limit of the traditional heat-insulating material cannot reach ultra-high temperature, and prepare the ultra-high temperature heat-insulating material with good ultra-high temperature thermal stability (> 2000 ℃), light weight and low thermal conductivity so as to meet the important requirements in the field of aerospace.
The technical scheme of the invention is as follows:
an ultra-light medium-entropy carbide ultra-high-temperature heat-insulating material is characterized in that the chemical formula of the carbide is (Ti) according to molar ratio x Zr y Nb 1-x-y ) C, wherein: 0<x<1，0<y<1，And x + y<1; porous (Ti) x Zr y Nb 1-x-y ) The porosity of C is 85-96%, and the highest temperature resistance is higher than 2000 ℃.
The ultra-light medium-entropy carbide ultra-high temperature heat insulation material has the advantages of light weight, high strength and low heat conductivity, and the density is 0.25-0.95 g/cm 3 The compression strength is 1-10 MPa, and the thermal conductivity is 0.125-0.395W/(m.K).
The ultra-light medium-entropy carbide ultra-high temperature heat-insulating material has the pore size distribution of 30-600 mu m and the average pore diameter of 50-300 mu m.
The preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat-insulating material comprises the following specific steps:
(1) Preparing slurry: adding a dispersing agent into deionized water, adding titanium carbide powder, zirconium carbide powder, niobium carbide powder and a sintering aid, and stirring to obtain uniformly mixed slurry;
(2) Foaming-pouring coagulation: heating the slurry obtained in the step (1), adding a foaming agent, quickly stirring and foaming, then adding a gelling agent and a surfactant, uniformly stirring, and then injecting the foam slurry into a mold;
(3) And (3) freeze drying: quickly freezing the foam slurry obtained in the step (2) at a low temperature, and then drying in vacuum to obtain a blank;
(4) And (3) high-temperature sintering: and (4) sintering the blank obtained in the step (3) at a high temperature to prepare the ultra-light medium-entropy ultra-high temperature heat-insulating material.
In the preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulation material, in the step (1), the particle size of the powder of titanium carbide, zirconium carbide and niobium carbide is 0.1-10 mu m; the sintering auxiliary agent is one or more than two of tungsten carbide, molybdenum silicide, silicon nitride, silicon carbide and zirconium silicide powder, and the particle size range is 0.1-10 mu m; the dispersant is citric acid, polyacrylic acid, ammonium citrate or polyacetyl imine.
According to the preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulation material, in the slurry in the step (1), the addition amount of the dispersing agent is 0.1-5 wt%, the addition amount of the mixed carbide powder is 5-60 wt%, the addition amount of the sintering aid is 0.1-10 wt%, and the balance is deionized water.
In the step (2), the foaming agent is sodium dodecyl sulfate or sodium dodecyl sulfate, the gelling agent is gelatin, agar or acrylamide, and the surfactant is stearic acid, polyethylene glycol or glycerol.
The preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulation material comprises the step (2) of adding 0.1-10 wt% of foaming agent, 0.2-10 wt% of gelling agent and 0.1-10 wt% of surfactant into the foam slurry.
In the step (3), the low-temperature quick freezing is performed at the temperature of-5 to-75 ℃ for 1 to 72 hours, and the ultra-light medium-entropy carbide ultra-high temperature heat-insulating material is dried in vacuum for 6 to 72 hours.
The preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulation material comprises the following steps of (4), pre-sintering is carried out, the pre-sintering condition is that the temperature is kept at 1300-1600 ℃ for 0.5-5 h, and the used atmosphere is nitrogen, argon or vacuum; and then high-temperature sintering is carried out, the temperature is kept for 1 to 5 hours under the high-temperature sintering condition of 1700 to 2200 ℃, and the used atmosphere is nitrogen, argon or vacuum.
The design idea of the invention is as follows:
in order to meet the goals of weight reduction and super heat insulation of parts in the field of aerospace ultrahigh-temperature thermal protection, the invention firstly selects titanium carbide (4.91 g/cm) with the lowest density in carbide ultrahigh-temperature ceramics 3 ) And zirconium carbide (6.59 g/cm) 3 ) And niobium carbide (6.3W/(m.K)) with the lowest thermal conductivity is taken as a raw material, and the intrinsic thermal conductivity of the matrix superhigh-temperature ceramic is remarkably reduced by utilizing multi-principal-element solid solution. Then, the foaming-pouring-freezing-drying technology is adopted to realize the ultrahigh porosity (85-96%) of the material, and break through the density and thermal conductivity limits of the ultrahigh-temperature ceramic. Finally preparing the ultra-high temperature resistant>2000 deg.C), super light (0.25-0.95 g/cm) 3 ) A novel ultra-high temperature super heat-insulating material with low heat conductivity (0.125-0.395W/(m.K)) and high strength (1-10 MPa).
The invention has the advantages and beneficial effects that:
1. adopts a new foaming-pouring-freeze drying technology to realize the ultra-high porosity (85-96 percent), thereby realizing the ultra-light weight (0.25-0.95 g/cm) 3 ) The object of (1).
2. The ultra-light medium-entropy carbide ultra-high temperature heat-insulating material has the characteristics of light weight and high strength (1-10 MPa), and solves the essential contradiction between high porosity and high strength.
3. The invention has simple process, convenient operation, short preparation period, high product performance and convenient conversion into productivity.
Drawings
FIG. 1 shows (Ti) in example 1 1/3 Zr 1/3 Nb 1/3 ) C X-ray diffraction spectrum of the porous ceramic.
FIG. 2 shows (Ti) in example 2 1/6 Zr 2/6 Nb 3/6 ) And C, scanning electron microscope photo of the porous ceramic.
FIG. 3 shows (Ti) in example 3 2/4 Zr 1/4 Nb 1/4 ) C, three-dimensional stereo topography of the porous ceramic.
Detailed Description
In the specific implementation process, the preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat-insulating material comprises the following steps: firstly, titanium carbide, zirconium carbide and niobium carbide powder are used as raw materials to prepare uniformly mixed slurry, then foaming, injection molding, freezing and vacuum drying are carried out, and finally high-temperature sintering is carried out, so that the titanium-zirconium-niobium ternary medium-entropy carbide ultra-high temperature heat insulation material with ultrahigh porosity and ultra-light weight is prepared.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, but the scope and implementation of the present invention are not limited thereto.
Example 1
In this embodiment, the preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulating material is as follows:
21 g of deionized water, 2.5 g of polyacrylic acid, 30 g of mixed powder (with the particle size of 1-5 microns) of titanium carbide, zirconium carbide and niobium carbide and 2 g of molybdenum silicide (with the particle size of 1-5 microns) are respectively weighed according to the molar ratio of 1And stirred for 3 hours to form a slurry in which the ceramic particles are uniformly dispersed. Then the slurry is heated and added with 3 g of sodium dodecyl sulfate, quickly and mechanically stirred and foamed for 10 minutes, then added with 2 g of gelatin gel and 1g of polyethylene glycol, and continuously stirred for 25 minutes and then injected into a mold. The injection molded ceramic foam body and mold were then placed in a-20 ℃ freezer for low temperature freezing for 24 hours, followed by vacuum drying for 72 hours, after which the body was demolded. Then sintering in vacuum of a lower tube furnace at 1450 ℃ for 3.5 hours, and finally sintering at high temperature in argon atmosphere in a carbon tube furnace at 2100 ℃ for 1.5 hours to finally prepare the high-porosity and ultrahigh temperature resistant (>2000 ℃ C. (Ti) 1/3 Zr 1/3 Nb 1/3 ) C, porous ceramic ultra-high temperature heat insulation material.
In this example, (Ti) 1/3 Zr 1/3 Nb 1/3 ) The porosity of the C porous ceramic was 88.7%, and the density was 0.75g/cm 3 The compressive strength was 8.1MPa. The sample phase composition is shown by XRD spectrum in attached figure 1, and it can be seen from the figure that the prepared porous material is nearly pure Ti-Zr-Nb ternary carbide solid solution phase (the peak types of TiC, zrC and NbC are the same, but the peak positions are slightly different, if not solid solution, the peak of each carbide single phase is near each peak in XRD pattern).
Example 2
In this embodiment, the preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulating material is as follows:
40 g of deionized water, 4 g of polyimide, 40 g of titanium carbide, zirconium carbide and niobium carbide mixed powder (the particle size is 3-7 microns) and 1g of silicon carbide (the particle size is 3-7 microns) in a molar ratio of 1. The slurry was then heated and 2 grams of sodium lauryl sulfate was added, foamed by rapid mechanical stirring for 15 minutes, then 5 grams of gelling agent agar and 2 grams of stearic acid were added, and injection molded after continued stirring for 40 minutes. The injection molded ceramic foam body and the mold were then placed in a freezer at-40 ℃ for low temperature freezing for 10 hours, followed by vacuum drying for 24 hours, after which the body was demolded. Finally, the process is carried out in vacuum in a tube furnace at 1300 DEG CSintering for 4 hours, then sintering at high temperature for 2 hours in a carbon tube furnace at 1950 ℃ under the atmosphere of argon, and finally preparing the high-porosity and ultrahigh temperature resistant product (>At 2000 ℃ of (Ti) 1/6 Zr 2/6 Nb 3/6 ) C, porous ceramic ultra-high temperature heat insulation material.
In this example, (Ti) 1/6 Zr 2/6 Nb 3/6 ) The porosity of the C porous ceramic was 92.9%, and the density was 0.49g/cm 3 The compressive strength was 2.2MPa, and the thermal conductivity was 0.161W/(m.K). The microscopic morphology of the sample is shown in the SEM photograph of FIG. 2, with a pore size distribution of 81-227 μm and an average pore size of about 146 μm.
Example 3
In this embodiment, the preparation method of the ultra-light medium-entropy carbide ultra-high temperature heat insulating material is as follows:
23 g of deionized water, 1g of ammonium citrate, 17g of mixed powder (with the particle size of 0.5-3 microns) of titanium carbide, zirconium carbide and niobium carbide and 0.5 g of silicon nitride (with the particle size of 0.5-3 microns) in a molar ratio of 2. Then the slurry is heated and added with 0.5 g of sodium dodecyl sulfate, quickly and mechanically stirred and foamed for 20 minutes, then added with 2 g of gelatin gel and 1g of glycerol, and continuously stirred for 30 minutes and then injection molded. The injection molded ceramic foam body and the mold were placed in a freezer at-65 ℃ for low temperature freezing for 10 hours, followed by drying in vacuum for 6 hours, after which the body was demolded. Finally sintering in 1500 ℃ lower tube furnace vacuum for 2 hours, then sintering at 1750 ℃ for 5 hours in the carbon tube furnace under nitrogen atmosphere, and finally preparing the high-porosity and ultrahigh temperature resistant (>2000 ℃ C. (Ti) 2/4 Zr 1/4 Nb 1/4 ) C, porous ceramic ultra-high temperature heat insulation material.
In this example, (Ti) 2/4 Zr 1/4 Nb 1/4 ) The porosity of the C porous ceramic was 95.5%, and the density was 0.27g/cm 3 The compressive strength was 1.1MPa, the thermal conductivity was 0.136W/(m.K), the pore size distribution of the sample was 96 to 329 μm, and the average pore diameter was about 213 μm.
As shown in fig. 3, from (Ti) 2/4 Zr 1/4 Nb 1/4 ) As can be seen from the three-dimensional topography of the C porous ceramic, the sample has a uniformly distributed and interconnected open pore structure, and is mainly macroporous with the pore diameter of 50-300 mu m. According to the reconstructed space distribution model, the porosity of the sample is 93%, which is close to the porosity of 95.5% calculated by an Archimedes formula, and the skeleton of the sample is relatively compact, so that the mechanical property of the material is enhanced.
The embodiment result shows that the ultra-light medium-entropy carbide ultra-high temperature heat insulation material has the characteristics of ultra-low density, high strength, low thermal conductivity and ultra-high temperature resistance, and has a wide application prospect in the field of aerospace ultra-high temperature heat insulation. The method has low cost and simple operation, and is suitable for large-scale industrial production.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions and combinations that are made without departing from the spirit and principle of the present invention should be considered as equivalent substitutions within the scope of the present invention.
Claims (10)
1. An ultra-light medium-entropy carbide ultra-high-temperature heat-insulating material is characterized in that the chemical formula of carbide is (Ti) according to molar ratio x Zr y Nb 1-x-y ) C, wherein: 0<x<1，0<y<1, and x + y<1; porous (Ti) x Zr y Nb 1-x-y ) The porosity of C is 85-96%, and the highest temperature resistance is higher than 2000 ℃.
2. The ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material of claim 1, wherein the thermal insulation material has advantages of light weight, high strength and low thermal conductivity, and has a density of 0.25-0.95 g/cm 3 The compression strength is 1-10 MPa, and the thermal conductivity is 0.125-0.395W/(mK).
3. The ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material according to claim 1, wherein the pore size distribution of the thermal insulation material is 30-600 μm, and the average pore diameter is 50-300 μm.
4. The preparation method of the ultra-light medium-entropy carbide ultra-high temperature thermal insulation material as claimed in any one of claims 1 to 3, is characterized by comprising the following steps:
(1) Preparing slurry: adding a dispersing agent into deionized water, adding titanium carbide powder, zirconium carbide powder, niobium carbide powder and a sintering aid, and stirring to obtain uniformly mixed slurry;
(2) Foaming-pouring coagulation: heating the slurry obtained in the step (1), adding a foaming agent, quickly stirring and foaming, then adding a gelling agent and a surfactant, uniformly stirring, and then injecting the foam slurry into a mold;
(3) And (3) freeze drying: quickly freezing the foam slurry obtained in the step (2) at a low temperature, and then drying in vacuum to obtain a blank;
(4) And (3) high-temperature sintering: and (4) sintering the blank obtained in the step (3) at a high temperature to prepare the ultra-light medium-entropy ultra-high temperature heat-insulating material.
5. The method for preparing the ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material according to claim 4, wherein in the step (1), the powder particle size of titanium carbide, zirconium carbide and niobium carbide is 0.1-10 μm; the sintering aid is one or more than two of tungsten carbide, molybdenum silicide, silicon nitride, silicon carbide and zirconium silicide powder, and the particle size range is 0.1-10 mu m; the dispersant is citric acid, polyacrylic acid, ammonium citrate or polyacetyl imine.
6. The preparation method of the ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material as claimed in claim 4, wherein in the slurry in the step (1), the addition amount of the dispersing agent is 0.1-5 wt%, the addition amount of the mixed carbide powder is 5-60 wt%, the addition amount of the sintering aid is 0.1-10 wt%, and the balance is deionized water.
7. The preparation method of the ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material as claimed in claim 4, wherein in the step (2), the foaming agent is sodium dodecyl sulfate or sodium dodecyl sulfate, the gelling agent is gelatin, agar or acrylamide, and the surfactant is stearic acid, polyethylene glycol or glycerol.
8. The preparation method of the ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material as claimed in claim 4, wherein in the foam slurry in the step (2), the addition amount of the foaming agent is 0.1-10 wt%, the addition amount of the gelling agent is 0.2-10 wt%, and the addition amount of the surfactant is 0.1-10 wt%.
9. The method for preparing the ultra-lightweight mid-entropy carbide ultra-high temperature thermal insulation material according to claim 4, wherein in the step (3), the low-temperature rapid freezing is performed at a temperature of-5 to-75 ℃ for 1 to 72 hours, and the material is dried in vacuum for 6 to 72 hours.
10. The preparation method of the ultra-light mid-entropy carbide ultra-high temperature heat-insulating material according to claim 4, characterized in that in the step (4), pre-sintering is carried out firstly, the pre-sintering condition is that the temperature is kept at 1300-1600 ℃ for 0.5-5 h, and the used atmosphere is nitrogen, argon or vacuum; and then high-temperature sintering is carried out, the temperature is kept for 1 to 5 hours under the high-temperature sintering condition of 1700 to 2200 ℃, and the used atmosphere is nitrogen, argon or vacuum.
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| CN202210964331.1A CN115368163A (en) | 2022-08-11 | 2022-08-11 | Ultra-light medium-entropy carbide ultra-high temperature heat insulation material and preparation method thereof |
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