CN114455978A - Fiber-reinforced mullite-proportioned oxide-modified phenolic resin aerogel composite material and preparation method thereof - Google Patents
Fiber-reinforced mullite-proportioned oxide-modified phenolic resin aerogel composite material and preparation method thereof Download PDFInfo
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- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material and a preparation method thereof. The composite material consists of a mullite proportioning oxide modified phenolic resin aerogel matrix and a high-temperature-resistant inorganic fiber reinforcing phase dispersed in the matrix, the shape of the composite material can be designed at will, and the composite material has the advantages of light weight, high strength, ablation resistance, heat insulation and the like, is particularly suitable for being used as a thermal protection material in the field of aerospace, and is simple in preparation process, low in raw material cost and beneficial to large-scale production.
Description
Technical Field
The invention relates to a thermal protection material and a preparation method thereof, in particular to a fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material with light weight, high strength, ablation resistance and heat insulation performance, and a preparation method thereof, belonging to the technical field of aerospace thermal protection materials.
Background
During the return of spacecraft or other aircraft to the atmosphere or during high-speed flight of the atmosphere, compressed air and frictional air generate a great deal of aerodynamic heat, the temperature is as high as hundreds or even thousands of degrees centigrade, and the exterior of the aircraft faces serious heating and ablation problems. Effective thermal protection and management of the aircraft exterior is therefore necessary to protect the aircraft structure and the internal equipment. A typical example of a reusable thermal protection system is the ceramic tile of the american space shuttle, which is a non-ablative ceramic foam with the disadvantages of high cost and low strength. The disposable resin thermal protection system of ablation-resistant type is emerging at present, which is characterized by micro-ablation, but is cheap and has high strength. The general traditional resin thermal protection composite material has too high density and thermal conductivity, and the surface shape of the structure at a high temperature line is difficult to maintain, so that the requirements of light weight, high strength, ablation resistance and heat insulation are difficult to adapt. The light phenolic resin impregnated carbon ablation material developed by NASA and related domestic departments in the United states has low density and low thermal conductivity, has good strength, ablation resistance and thermal insulation performance in a harsh high-altitude thermal environment, is successfully applied to star dust, the heat-proof outsole of a 'Dragon' freight ship of SpaceX company and related domestic tests, effectively reduces the weight of the aircraft body and improves the effective load.
There are many similar related patents at home and abroad, for example, chinese patent (application No. 201811354373.3) discloses an organic-inorganic dual-network phenolic/alumina aerogel composite material and a preparation method thereof, but the patent needs to add a powder opacifier to improve the heat insulation performance, and the powder opacifier is easily blocked by reinforcing fibers and is not uniformly dispersed, so that a good heat insulation effect cannot be achieved. For another example, chinese patent (application No. 201911266938.7) discloses a high-strength nanoporous ceramic ablative heat-proof composite material and a preparation method thereof, which relates to an organosilicon hybrid phenolic resin, which does not introduce mullite and other high-temperature-resistant components and has a poor ablation-resistant effect.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a composite material which takes mullite proportioning oxide modified phenolic resin aerogel as a matrix and takes high-temperature-resistant inorganic fibers as a reinforcing phase, and the composite material has excellent comprehensive properties such as light weight, high strength, ablation resistance, heat insulation and the like, and the density is 0.3-1.1 g/cm3(ii) a The tensile strength is 10-100 MPa, and the ablation rate of the wire is 0.004-0.05 mm/s under the condition that the flame spray gun ablates for 600s at 1300 ℃; the thermal conductivity is 0.03-0.07W/m.K, and the material can be widely applied to the field of aerospace as a thermal protection material.
The second purpose of the invention is to provide a preparation method of the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material, which has the advantages of simple process, low raw material cost and contribution to large-scale production.
In order to achieve the technical purpose, the invention provides a fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material which comprises a mullite proportion oxide modified phenolic resin aerogel matrix and a high-temperature-resistant inorganic fiber reinforcement phase dispersed in the matrix.
The shape of the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material provided by the invention can be designed according to needs, and can be a plate or a complex shape, the thickness is between 3 mm and 100mm, and the thickness is preferably between 9 mm and 20 mm.
The fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material takes the organic phenolic resin aerogel as a base material, has the characteristic of light weight, and has the density of 0.3-1.1 g/cm3The density is preferably 0.45 to 0.65g/cm3The density of the heat-proof and heat-insulating material is lower in the same class, and the weight-reducing effect is achieved. The high-temperature-resistant inorganic fibers are uniformly dispersed in the composite material, not only are the composite material endowed with good high-temperature resistance and ablation resistance, but also the mechanical properties of the composite material can be greatly improved, the tensile strength of the composite material is 10-100 MPa, the tensile strength is preferably 20-30 MPa, and the strength of similar common materials is generally less than 10 MPa. Meanwhile, mullite proportioning oxides are uniformly dispersed in the composite material, the mullite proportioning oxides are uniformly dispersed in the phenolic resin aerogel and can generate a mullite phase through a chemical reaction at high temperature, the mullite proportioning oxides can block oxygen from entering, so that the oxidation resistance of the material is improved, the ablation resistance is improved, the linear ablation rate is 0.004-0.05 mm/s, preferably 0.006-0.02 mm/s, the thermal conductivity is 0.03-0.07W/m.K, preferably 0.04-0.05W/m.K under the condition that a flame spray gun ablates for 600s at 1300 ℃, and the thermal conductivity of the similar common material is generally more than 0.08W/m.KThe material has excellent comprehensive properties of light weight, high strength, ablation resistance, heat insulation and the like.
As a preferable scheme, the mass percentage of the mullite proportion oxide modified phenolic resin aerogel matrix and the high-temperature resistant inorganic fiber reinforcement phase in the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material is 45-75%: 25-55%. The mass percentage composition of the mullite-prepared oxide-modified phenolic resin body and the high-temperature-resistant inorganic fiber reinforced phase is further preferably 55-70%: 30-45%, generally speaking, the higher the reinforcement of the high-temperature resistant inorganic fiber, the more excellent the mechanical properties, but also the density and the thermal conductivity coefficient are affected, so the proportion of the two must be coordinated, and a composite material with high mechanical strength, low density and good thermal conductivity can be obtained.
As a preferable scheme, the mass percentage composition of the phenolic resin and the mullite proportioning oxide in the mullite proportioning oxide modified phenolic resin body is as follows: 60-90% and 10-40%. The mass percentage composition of the phenolic resin and mullite proportioning oxide is further preferably as follows: 70-80% and 20-30%. Generally, too low a content of mullite proportion oxide does not improve the high temperature resistance, but too high a content of mullite proportion oxide sacrifices the heat insulation effect of the composite material and increases the density.
As a preferable scheme, Al in the mullite proportioning oxide2O3And SiO2In a molar ratio of 3: 2. The mullite is mixed with 3Al2O3:2SiO2The prepared form of the mullite is present in the composite material, and the mullite prepared oxide is converted into a mullite phase in the environment of more than 1100 ℃.
Preferably, the high-temperature resistant inorganic fiber reinforcing phase is a needle felt or a woven body made of at least one of quartz fibers, high silica fibers, aluminum silicate fibers, mullite fibers and carbon fibers. The high-temperature resistant inorganic fiber existing in the form of a needle felt or a woven body is obviously improved in mechanical property compared with single fiber.
As a preferable scheme, the mullite proportion oxide modified phenolic resin aerogel matrix comprises nanopores with the pore diameter within the range of 10-100 nm, and mullite proportion oxide is uniformly dispersed in the nanopores. The preferred nanometer aperture distribution in the phenolic resin aerogel is 20-50 nm. The mullite proportioning oxide is highly dispersed in the phenolic resin aerogel in a nano-particle form, and has higher reaction activity.
The invention also provides a preparation method of the fiber-reinforced mullite proportioning oxide modified phenolic resin aerogel composite material, which comprises the following steps:
1) according to Al in mullite2O3And SiO2Preparing mullite sol according to the proportion requirement;
2) mixing the mullite sol with phenolic resin, and adding a curing agent to fully dissolve to obtain a precursor solution;
3) placing high-temperature-resistant inorganic fiber in an inner cavity of a mold, vacuumizing the inner cavity of the mold, sucking a precursor solution into the inner cavity of the mold by utilizing a vacuum environment, and heating and curing
4) After solidification, discharging gas or liquid in the mould, opening the mould and drying to obtain the product. .
According to the technical scheme, the mullite sol is mixed with the phenolic resin, so that the mullite sol can be uniformly dispersed in the phenolic resin, a precursor solution with good stability can be formed, the subsequent die forming process is facilitated, and the stability of mass production is greatly improved.
As a preferable scheme, the mullite component in the mullite sol is 15-28% by mass.
As a preferred scheme, the curing agent is urotropin and/or melamine; the mass of the curing agent is 6-18% of that of the phenolic resin.
As a preferred embodiment, the curing conditions are: the temperature is 80-160 ℃, and the time is 30-60 hours.
As a preferred scheme, the mullite sol takes small molecular alcohols as a solvent.
The preparation method of the fiber-reinforced mullite proportioning oxide modified phenolic resin aerogel composite material comprises the following steps:
step 1): preparing an alcohol solvent mullite sol: preparing mullite sol with ethanol or isopropanol as a solvent according to a mullite proportion, wherein the content of the mullite in the sol is 15-28%, and the preferable content is 18-25%.
Step 2): mixing phenolic resin and the mullite sol in a proper proportion, wherein the mass percentage of the phenolic resin and the mullite matching oxide is as follows: 60-90% and 10-40%, heating and stirring at about 50 deg.C to dissolve; the normal temperature stable period of the mixture of the phenolic resin and the mullite sol is more than 6 months, which is longer than that of the mixture of the similar resin solution and the silica sol or the alumina sol.
Step 3): adding urotropine or melamine curing agent into the solution obtained in the step 2) according to 6-18% of the weight of the phenolic aldehyde, preferably 9-14%, heating to about 50 ℃, and stirring to dissolve for later use.
Step 4): the inorganic fiber needled felt or fabric is placed in a metal mold which can be closed and evacuated.
Step 5): vacuumizing the mould, sucking the solution in the step 3), and closing the valve.
Step 6): and (3) heating the die at 80-160 ℃, preferably 100-130 ℃ for about 48 hours.
Step 7): opening the valve to discharge gas and liquid, opening the mold, and drying in an oven.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material provided by the invention has multiple functions of light weight, high strength, ablation resistance, heat insulation and the like, and the density of the composite material is 0.45-0.65 g/cm3The tensile strength is 20-30 MPa; the linear ablation rate of the composite material is between 0.006 and 0.02mm/s under the condition that the composite material is ablated for 600s at 1300 ℃ by a flame spray gun; the thermal conductivity is between 0.04 and 0.05W/m.K, and the shape of the composite material can be designed according to requirements and can be a plate or a complex materialThe shape and the thickness are between 9 and 20mm, and the material can be used as a thermal protection material and widely applied to the field of aerospace.
According to the preparation method of the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material, provided by the technical scheme of the invention, the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material with multiple excellent functions of light weight, high strength, ablation resistance, heat insulation and the like is successfully prepared by combining the mullite sol and the phenolic resin solution, the stability period of the phenolic resin is greatly prolonged, the preparation process is simplified, the raw material cost is low, and the large-scale production is facilitated.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the claims.
The starting materials mentioned in the following examples are, unless otherwise specified, commercially available reagents or synthetic starting materials which are reported in the literature.
Example 1
In this example, a composite material with mullite proportion oxide modified phenolic aerogel as a matrix and high temperature resistant inorganic fibers as a reinforcing phase was prepared. The method comprises the following steps:
step one, preparing 1000 g of mullite sol of 18 percent isopropanol solvent, wherein the solid content is 3Al2O3:2SiO2The molar ratio of (A) to (B).
Step two, 450 g of thermoplastic phenolic resin (purchased from Hebei Zetian chemical Co., Ltd.) is gradually dissolved in the sol under heating and stirring at about 50 ℃.
And step three, adding 45 g of urotropin into the solution obtained in the step two, heating and stirring at about 50 ℃, and dissolving for later use.
Cutting the quartz fiber needled felt according to the size of the inner cavity of the mould (200 multiplied by 18mm), weighing (130.5 g), and placing the quartz fiber needled felt in a closed carbon steel mould capable of being vacuumized.
And step five, vacuumizing the mould, fully sucking the solution in the step three, and closing a valve.
And step six, heating the mould at 100 ℃ for about 48 hours.
And step seven, opening the valve to discharge gas and liquid, opening the mold, and drying in an oven.
Tests prove that the normal-temperature stable period of the mixed solution of the mullite collosol and the phenolic resin in the embodiment is 195 days, and the problems of turbidity, precipitation, addition of the curing agent, difficulty in curing under a heating condition and the like do not occur in the period. The size of the material prepared according to the steps is 200 multiplied by 18 mm; the density was 0.52g/cm3(ii) a The tensile strength is 21 MPa; under the condition that the flame spray gun ablates for 600s at 1300 ℃, the ablation rate of the wire is 0.0065 mm/s; the thermal conductivity was 0.042W/m.K.
Comparative example 1
In this example, a composite material in which a phenolic aerogel without introducing a mullite proportion oxide is used as a matrix and a high-temperature-resistant inorganic fiber is used as a reinforcing phase is prepared. The method comprises the following steps:
step one, isopropanol with the same mass as that of 'example 1' is prepared, and a mullite sol component is not contained.
Step two, 450 g of thermoplastic phenolic resin (purchased from Hebei Zetian chemical Co., Ltd.) is gradually dissolved in the sol under heating and stirring at about 50 ℃.
And step three, adding 45 g of urotropin into the solution obtained in the step two, heating and stirring at about 50 ℃, and dissolving for later use.
Cutting the quartz fiber needled felt according to the size of the inner cavity of the mould (200 multiplied by 18mm), weighing (126.9 g), and placing the cut quartz fiber needled felt in a closed carbon steel mould capable of being vacuumized.
And step five, vacuumizing the mould, fully sucking the solution in the step three, and closing a valve.
And step six, heating the mould at 100 ℃ for about 48 hours.
And step seven, opening the valve to discharge gas and liquid, opening the mold, and drying in an oven.
The test shows that the mixed solution of the phenolic resin in the embodiment has the stability at normal temperatureThe period is 260 days, and the problems of turbidity, precipitation, addition of a curing agent, difficult curing under heating and the like do not occur in the period. The size of the material prepared according to the steps is 200 multiplied by 18 mm; the density was 0.46g/cm3(ii) a The tensile strength is 23 MPa; under the condition that the flame spray gun ablates for 600s at 1300 ℃, the line ablation rate is 0.075 mm/s; the thermal conductivity was 0.048W/m.K.
It can be seen from the comparative example that, the high-temperature ablation rate of the phenolic aerogel composite material without introducing the mullite proportioning oxide is enlarged by more than 10 times, and other performances are basically equivalent. Therefore, the introduction of the mullite proportioning oxide is very significant for improving the comprehensive performance of the phenolic aerogel composite material.
Example 2
In this example, a composite material with mullite proportion oxide modified phenolic aerogel as a matrix and high temperature resistant inorganic fibers as a reinforcing phase was prepared. The method comprises the following steps:
step one, 1500 g of mullite sol of 20% concentration isopropanol solvent is prepared, wherein the solid content is 3Al2O3:2SiO2The molar ratio of (A) to (B).
Step two, 900 g of thermoplastic phenolic resin (purchased from Hebei Zetian chemical Co., Ltd.) is gradually dissolved in the sol under heating and stirring at about 50 ℃.
And step three, adding 80 g of urotropine into the solution obtained in the step two, heating and stirring at about 50 ℃, and dissolving for later use.
Cutting the alumina fiber needled felt according to the size of the inner cavity of the mould (200 multiplied by 18mm), weighing (146.4 g), and placing the alumina fiber needled felt in a closed carbon steel mould capable of being vacuumized.
And step five, vacuumizing the mould, fully sucking the solution in the step three, and closing a valve.
And step six, placing the die at 130 ℃ and heating for about 48 hours.
And step seven, opening the valve to discharge gas and liquid, opening the mold, and drying in an oven.
Tests prove that the mixed solution of the mullite collosol and the phenolic resin in the embodiment has the normal-temperature stable period ofAnd the problems of turbidity, precipitation, addition of a curing agent, difficult curing under heating and the like do not occur in 203 days. The size of the material prepared according to the steps is 200 multiplied by 18 mm; the density was 0.55g/cm3(ii) a The tensile strength is 27 MPa; under the condition that the flame spray gun ablates for 600s at 1300 ℃, the ablation rate of the wire is 0.0071 mm/s; the thermal conductivity was 0.045W/m.K.
Example 3
In this example, a composite material with mullite proportion oxide modified phenolic aerogel as a matrix and high temperature resistant inorganic fibers as a reinforcing phase was prepared. The method comprises the following steps:
step one, 1200 g of mullite sol of isopropanol solvent with the concentration of 15 percent is prepared, wherein the solid content is 3Al2O3:2SiO2The molar ratio of (A) to (B).
Step two, 500 g of thermoplastic phenolic resin (purchased from Hebei Zetian chemical Co., Ltd.) is gradually dissolved in the sol under heating and stirring at about 50 ℃.
And step three, adding 50 g of urotropine into the solution obtained in the step two, heating and stirring at about 50 ℃, and dissolving for later use.
Cutting the mullite fiber needled felt according to the size of the inner cavity of the mould (200 multiplied by 18mm), weighing (138.9 grams), and placing the mullite fiber needled felt in a closed carbon steel mould capable of being vacuumized.
And step five, vacuumizing the mould, fully sucking the solution in the step three, and closing a valve.
Sixthly, the mold is placed at 110 ℃ and heated for about 48 hours.
And step seven, opening the valve to discharge gas and liquid, opening the mold, and drying in an oven.
Tests prove that the normal-temperature stable period of the mixed solution of the mullite collosol and the phenolic resin in the embodiment is 212 days, and the problems of turbidity, precipitation, addition of the curing agent, difficulty in curing under a heating condition and the like do not occur in the period. The size of the material prepared according to the steps is 200 multiplied by 18 mm; the density was 0.48g/cm3(ii) a The tensile strength is 20 MPa; under the condition that the flame spray gun ablates for 600s at 1300 ℃, the ablation rate of the wire is 0.0078 mm/s; the thermal conductivity is 0.044W/m·K。
Table 1 main performance indices of the composite materials obtained by way of example
Claims (10)
1. A fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material is characterized in that: consists of a mullite proportioning oxide modified phenolic resin aerogel matrix and a high-temperature resistant inorganic fiber reinforced phase dispersed in the matrix.
2. The fiber-reinforced mullite proportioned oxide modified phenolic resin aerogel composite material as claimed in claim 1, wherein: the mass percentage composition of the mullite proportioning oxide modified phenolic resin aerogel matrix and the high-temperature resistant inorganic fiber reinforcing phase in the fiber-reinforced mullite proportioning oxide modified phenolic resin aerogel composite material is 45-75%: 25-55%.
3. The fiber-reinforced mullite proportioned oxide modified phenolic resin aerogel composite material according to claim 1 or 2, wherein: the mass percentage of the phenolic resin and the mullite proportioning oxide in the mullite proportioning oxide modified phenolic resin aerogel matrix is as follows: 60-90% and 10-40%.
4. The fiber-reinforced mullite proportioned oxide modified phenolic resin aerogel composite material as claimed in claim 3, wherein: al in the mullite proportioning oxide2O3And SiO2In a molar ratio of 3: 2.
5. The fiber-reinforced mullite proportioned oxide modified phenolic resin aerogel composite material as claimed in claim 2, wherein: the high-temperature resistant inorganic fiber reinforced phase is a needled felt or a knitted body composed of at least one of quartz fiber, high silica fiber, aluminum silicate fiber, mullite fiber and carbon fiber.
6. The fiber-reinforced mullite proportioned oxide modified phenolic resin aerogel composite material as claimed in claim 1, wherein: the mullite proportion oxide modified phenolic resin aerogel matrix contains nano holes with the aperture within the range of 10-100 nm, and mullite proportion oxide is uniformly dispersed in the nano holes.
7. The preparation method of the fiber-reinforced mullite proportion oxide modified phenolic resin aerogel composite material as claimed in any one of claims 1 to 6, characterized by comprising the following steps: the method comprises the following steps:
1) according to Al in mullite2O3And SiO2Preparing mullite sol according to the proportion requirement;
2) mixing the mullite sol with phenolic resin, and adding a curing agent to fully dissolve to obtain a precursor solution;
3) placing high-temperature-resistant inorganic fibers in an inner cavity of a mold, vacuumizing the inner cavity of the mold, sucking a precursor solution into the inner cavity of the mold by utilizing a vacuum environment, and heating and curing;
4) after solidification, discharging gas or liquid in the mould, opening the mould and drying to obtain the product.
8. The preparation method of the fiber-reinforced mullite proportioning oxide modified phenolic resin aerogel composite material as claimed in claim 7, wherein: the mass percentage content of the mullite component in the mullite sol is 15-28%.
9. The preparation method of the fiber-reinforced mullite proportioning oxide modified phenolic resin aerogel composite material as claimed in claim 7, wherein: the curing agent is urotropine and/or melamine; the mass of the curing agent is 6-18% of that of the phenolic resin.
10. The preparation method of the fiber-reinforced mullite proportioning oxide modified phenolic resin aerogel composite material as claimed in claim 7, wherein: the curing conditions are as follows: the temperature is 80-160 ℃, and the time is 30-60 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115387119A (en) * | 2022-09-02 | 2022-11-25 | 北京交通大学 | Light dredging-heat insulation hybrid woven thermal protection material and preparation method thereof |
| CN117466569A (en) * | 2023-12-28 | 2024-01-30 | 北京玻钢院复合材料有限公司 | Honeycomb structure reinforced aerogel-phenolic resin matrix composite material and preparation method thereof |
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