CN109354823B - Preparation method of heat-insulation ceramizable phenolic resin-based gradient composite material - Google Patents
Preparation method of heat-insulation ceramizable phenolic resin-based gradient composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a heat-insulation ceramic phenolic resin-based gradient composite material. Respectively soaking fiber cloth serving as a reinforcing phase in different gum dipping solutions with phenolic resin serving as a matrix, ceramic components and hollow microsphere content in gradient distribution to prepare a prepreg; laminating, die pressing, and thermosetting at 150-200 deg.C to obtain the gradient composite material containing heat-proof layer, gradient transition layer and heat-insulating layer. When the temperature of the gradient composite material prepared by the invention is up to 1000 ℃, the heat-proof layer can be converted into a ceramic phase with higher strength, and the heat flow scouring can be resisted; the gradient transition layer can relieve stress concentration and reduce stress; the hollow microspheres are added, so that the heat insulation layer has good heat matching performance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a heat-insulation ceramizable phenolic resin-based gradient composite material.
Background
The gradient material is a composite material with the properties of the material showing gradient changes corresponding to the continuous change of the components and the microstructure in space. Compared with the traditional composite material, because the phases of the composition gradient material have continuous and smooth transition, when the gradient material is added between the interfaces of two different materials, the problem of thermal mismatch between the interfaces of the materials can be greatly relieved, and the peeling damage of the whole material at the interfaces of the different materials can be avoided.
At present, a plurality of preparation processes for preparing gradient materials are available, for example, the gradient/heat-proof ceramic matrix composite material and the preparation method thereof disclosed by the publication number CN101391895A are prepared by powder molding: raw material powder bodies which are subjected to ultrasonic cleaning, ball milling and drying and used for preparing each layer are sequentially paved in a graphite mold, and the mixture is heated and then is kept warm for 5 minutes under the inert atmosphere condition to obtain the material. The powder molding is influenced by factors such as uneven material weight, poor material flowability, uncontrollable operation and the like, so that the sample is easy to generate defects.
The gradient heat-proof material and the preparation method thereof are disclosed in the publication number CN105294143A, and the gradient heat-proof material is prepared by an amorphous SiCO reinforced porous ceramic material matrix, a silicon boron glass intermediate and a surface coating made of an oxidation material. The sample prepared by the method is easy to generate large stress at the position between layers.
The polymer-based composite material can be subjected to a ceramic technology, and is a novel way for improving the high temperature resistance, ablation resistance and scouring resistance of the polymer-based composite material. For example, publication No. CN 102675822 discloses a ceramifiable carbon-based polymer composite material and a preparation method thereof, which is prepared by mixing and pressing carbon-based resin, a high-temperature resistant coupling agent, a fiber reinforced material, aluminosilicate mineral powder and non-oxidative ceramic powder. For example, a flame-retardant ceramizable polymer composite material disclosed in publication number CN104945838A is prepared by adding ceramizable additives into a novel ablation-resistant polymer/resin, and impregnating and press-molding the mixture.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-heat-insulation ceramizable phenolic resin-based gradient composite material. Particularly, the inner layer structure of the aircraft is protected from being damaged under the thermal environment of high heat flow and high scouring of single side of components such as an outer shell of the aerospace aircraft, the requirement of the aerospace aircraft for integration of heat insulation and prevention under the high thermal environment is met, and the reliability of the thermal protection of the components of the advanced aerospace aircraft is improved.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of an anti-heat insulation ceramizable phenolic resin based gradient composite material comprises the following steps;
respectively soaking fiber cloth serving as a reinforcing phase in different gum dipping solutions with phenolic resin serving as a matrix, ceramic components and hollow microsphere content in gradient distribution to prepare a prepreg; laminating, mould pressing, and thermosetting at 150-200 ℃ to obtain a gradient composite material comprising a heat-proof layer, a gradient transition layer and a heat-insulating layer;
wherein the mass percent of the ceramic components in the dipping solution is reduced in a gradient manner according to 50-0%, and the mass percent of the cenospheres is increased in a gradient manner according to 0-4.8%.
According to the scheme, the fiber cloth comprises one or more of quartz fiber cloth, carbon fiber cloth and high silica cloth.
According to the scheme, the phenolic resin is boron phenolic resin.
According to the scheme, the hollow microspheres are one or more of hollow glass microspheres, hollow ceramic microspheres and phenolic resin hollow microspheres; the particle size is 10 to 250 μm, and the bulk density is 0.35 to 0.45g/cm3。
According to the scheme, the ceramic component is one or more of silicide-based metal ceramic, kaolin, silicon dioxide and mica; d50The particle size is 2-3 um, and the purity is more than 99%.
According to the scheme, the impregnation solution for preparing the heat-proof layer comprises the following components: the ceramic component, the hollow microspheres, the resin and the solvent are mixed according to the mass ratio of 2:0:1: 1; the dip solution for preparing the gradient transition layer comprises the following components: the ceramic component, the hollow microspheres, the resin and the solvent are mixed according to the mass ratio of 1.5:0.025:1:1, 1:0.05:1:1 and 0.5:0.075:1: 1; the dip solution for preparing the heat insulation layer comprises the following components: the ceramic component, the hollow microspheres, the resin and the solvent are in a mass ratio of 0:0.1:1: 1.
According to the scheme, the thickness of the gradient composite material is controlled to be 10-11 mm.
When the temperature of the gradient composite material prepared by the invention is up to 1000 ℃, the heat-proof layer can be converted into a ceramic phase with higher strength, and the heat flow scouring can be resisted; the gradient transition layer can relieve stress concentration and reduce stress; addingThe hollow microspheres enable the heat-insulating layer to have good heat matching performance, and the density of the composite material can be controlled to be 0.7-1.2 g/cm according to design3Within the range, the integration of heat insulation and prevention is realized. The heat-insulation ceramic-prevention phenolic resin-based gradient composite material provided by the invention can protect the material from being damaged by high temperature when being heated in a single direction.
The invention realizes the function of integration of heat insulation and prevention by the design of preparing prepreg laminated mould pressing, namely, the surface layer is non-ablative and heat insulation, and the inner layer is heat insulation.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
Preparing materials: the weight portion of the material is as follows: 0 part, 5 parts, 10 parts, 15 parts and 20 parts of hollow microspheres, 200 parts, 150 parts, 100 parts, 50 parts and 0 part of ceramic components and 40 layers of fiber cloth.
5 groups were prepared by dissolving 100 parts of boron phenol resin and 100 parts of alcohol in a ratio of 1 to 1. The hollow microspheres and the ceramic components are respectively added into the solution and are uniformly stirred to prepare the gradient impregnation solution. Cutting regular fiber cloth, uniformly coating the dipping solution on the fiber cloth to prepare prepreg, and airing until the viscosity is proper.
Cutting the prepreg into regular size, and stacking the prepreg and the ceramic components in sequence from high to low to form 40 layers. Placing the composite material in a mould and placing the composite material on a hot press, and carrying out compression molding at the temperature of 80-200 ℃ and under the pressure of 15-19 MPa to obtain the ceramic-proof phenolic resin-based gradient composite material.
Example 2
The same as in example 1.
Weighing and trimming the prepared sample of the heat-insulation ceramizable phenolic resin-based gradient composite material, cutting the sample into a regular cube, and measuring the length, width and height of the material to obtain the material with the density of 1.1g/cm3。
Example 3
The same as in example 1.
The interface of the composite material is analyzed by an electron probe microanalyzer, and the gradient distribution of the titanium element can be observed. The preparation process is good, and the gradient composite material can be prepared.
Example 4
The same as in example 1.
The sample was machined to a phi 30 x 10mm ablation sample. In the air atmosphere, the samples were subjected to ablation testing using an oxyacetylene ablation machine, with 5 samples in a group and the line ablation rates averaged. The ablation rate of the sample is less than or equal to 0.015mm/s through the ablation test of oxyacetylene.
Example 5
The same as in example 1.
And (3) putting the prepared gradient composite material sample into a muffle furnace, performing a high-temperature thermal experiment at 1200 ℃, protecting the side surface and the inner layer of the sample by using insulating bricks and aerogel, and exposing only one side of the surface layer. After 10 minutes, the material has stable size, no obvious defect on the surface of the material, no thermal stress crack in the thickness direction, no obvious ablation on one side of the heat insulation layer, and good overall performance. The weight loss is more than or equal to 70 percent, and the heat conductivity from the heat-proof layer to the heat-insulating layer is less than 0.4W/mK.
Claims (6)
1. A preparation method of an anti-heat insulation ceramizable phenolic resin based gradient composite material is characterized by comprising the following steps;
respectively soaking fiber cloth serving as a reinforcing phase in different gum dipping solutions with phenolic resin serving as a matrix, ceramic components and hollow microsphere content in gradient distribution to prepare a prepreg; laminating, mould pressing, and thermosetting at 150-200 ℃ to obtain a gradient composite material comprising a heat-proof layer, a gradient transition layer and a heat-insulating layer;
wherein the mass percent of the ceramic components in the dipping solution is reduced according to a gradient of 50-0%, and the mass percent of the cenospheres is increased according to a gradient of 0-4.8%;
the fiber cloth is one or more of quartz fiber cloth, carbon fiber cloth and high silica cloth.
2. The method of claim 1, wherein the phenolic resin is a boro-phenolic resin.
3. The method for preparing the heat-proof and insulating gradient composite material based on the ceramifiable phenolic resin as claimed in claim 1, wherein the hollow microspheres are one or more of hollow glass microspheres, hollow ceramic microspheres and phenolic resin hollow microspheres; the particle size is 10 to 250 μm, and the bulk density is 0.35 to 0.45g/cm3。
4. The method for preparing the heat-proof ceramic-based phenolic resin gradient composite material as claimed in claim 1, wherein the ceramic component is one or more of montmorillonite, silica, mica and kaolin; d50The particle size is 2-3 um, and the purity is more than 99%.
5. The method for preparing the heat-proof and insulating ceramic phenolic resin-based gradient composite material as claimed in claim 1, wherein the dip solution for preparing the heat-proof layer comprises the following components: the ceramic component, the hollow microspheres, the resin and the solvent are mixed according to the mass ratio of 2:0:1: 1; the dip solution for preparing the gradient transition layer comprises the following components: the ceramic component, the hollow microspheres, the resin and the solvent are mixed according to the mass ratio of 1.5:0.025:1:1, 1:0.05:1:1 and 0.5:0.075:1: 1; the dip solution for preparing the heat insulation layer comprises the following components: the ceramic component, the hollow microspheres, the resin and the solvent are in a mass ratio of 0:0.1:1: 1.
6. The method for preparing the heat-insulating ceramifiable phenolic resin-based gradient composite material as claimed in claim 1, wherein the thickness of the gradient composite material is controlled to be 10-11 mm.
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| CN109910390B (en) * | 2019-03-04 | 2020-10-09 | 湖北菲利华石英玻璃股份有限公司 | Preparation method of gradient density resin composite material prefabricated body |
| CN109968757B (en) * | 2019-04-22 | 2020-07-07 | 中国人民解放军国防科技大学 | Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof |
| CN110194609B (en) * | 2019-04-22 | 2021-07-16 | 湖南远辉新材料研究院有限公司 | High-temperature-resistant and oxidation-resistant ceramizable resin composite material and preparation method thereof |
| CN112708240A (en) * | 2019-10-24 | 2021-04-27 | 洛阳双瑞橡塑科技有限公司 | Thermosetting ceramizable phenolic aldehyde composite material and preparation process thereof |
| CN110627517B (en) * | 2019-10-25 | 2022-03-25 | 航天特种材料及工艺技术研究所 | Gradient ultrahigh-temperature ceramic matrix composite material and preparation method thereof |
| CN112457039A (en) * | 2020-11-27 | 2021-03-09 | 尚天保 | Carbon fiber heat insulation material and preparation method thereof |
| CN112920442B (en) * | 2021-01-29 | 2023-04-07 | 中国人民解放军国防科技大学 | Resin-based heat-proof composite material with surface coated with high-temperature infrared stealth coating and preparation method thereof |
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| CN113276496B (en) * | 2021-06-03 | 2022-07-08 | 北京理工大学 | Light-weight heat-insulation integrated carbon fiber reinforced phenolic resin composite material |
| CN114311869A (en) * | 2021-12-30 | 2022-04-12 | 湖北三江航天红阳机电有限公司 | Low-density high-temperature-resistant heat-insulation-preventing composite material and preparation method thereof |
| CN115181393B (en) * | 2022-07-01 | 2023-06-23 | 蚌埠凌空科技有限公司 | Modified resin matrix composite material for heat insulation and preparation method thereof |
| CN115447218B (en) * | 2022-09-23 | 2023-11-17 | 湖北航天技术研究院总体设计所 | Surface porcelain reinforced light heat-proof and heat-insulating integrated structure and preparation method thereof |
| CN115816926B (en) * | 2022-12-22 | 2023-10-13 | 武汉理工大学 | Reusable heat-proof and heat-proof structure based on ceramic tile and preparation method thereof |
| CN117430912B (en) * | 2023-12-20 | 2024-07-05 | 中国科学院赣江创新研究院 | Expanded microsphere modified fiber reinforced phenolic aerogel composite material and preparation method and application thereof |
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| CN101259766A (en) * | 2008-04-18 | 2008-09-10 | 哈尔滨工业大学 | Polymer/porous ceramics structure and function integrated gradient composite material and preparation method thereof |
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| CN101259766A (en) * | 2008-04-18 | 2008-09-10 | 哈尔滨工业大学 | Polymer/porous ceramics structure and function integrated gradient composite material and preparation method thereof |
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| 树脂基热防护材料研究进展;王富忠等;《化工新型材料》;20121231;第40卷(第12期);1-3 * |
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