CN113845746A - Mesophase asphalt modified ablation-resistant resin matrix material and preparation method and application thereof - Google Patents
Mesophase asphalt modified ablation-resistant resin matrix material and preparation method and application thereof Download PDFInfo
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- 239000012779 reinforcing material Substances 0.000 claims description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
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- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
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- Chemical Kinetics & Catalysis (AREA)
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- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an intermediate phase asphalt modified ablation-resistant resin matrix material, a preparation method and application thereof, and belongs to the technical field of ablation-resistant materials. The composition is prepared from the following raw materials in parts by weight: 100-120 parts of ablation-resistant resin and 1-200 parts of mesophase pitch. The liquid state carbonization process of the mesophase pitch and the solid state carbonization process of the resin three-dimensional cross-linked network are combined in the ablation process of the material, and the mesophase pitch liquid crystal ordered carbon structure is introduced into the carbon layer, so that the generation of shrinkage cracks in the carbon layer is reduced, the graphitization degree of the carbon layer is increased, the anti-scouring performance of the material under the condition of high heat flow and oxygen enrichment is obviously improved, the formed carbon layer is more complete and compact, and the ablation resistance of the material is obviously improved. The material is suitable for preparing resin-based ablation heat-proof composite materials, and can be applied to the preparation of heat-proof structures of related equipment such as high-speed aircrafts, engines and the like so as to protect structures and parts which need to be subjected to severe environments such as high-temperature gas or pneumatic heat flow scouring and the like.
Description
Technical Field
The invention belongs to the technical field of ablation-resistant materials, and particularly relates to an intermediate phase asphalt modified ablation-resistant resin matrix material, and a preparation method and application thereof.
Background
As the service environment of aerospace and aviation equipment such as aircrafts and the like is extremely severe, the heat-resistant coating has very high requirements on ablation resistance, hot-flow scouring resistance, mechanical and mechanical properties and the like. The action mechanism of ablation resistance of the heat-resistant layer is that after the ablation-resistant material is heated, the heat is difficult to conduct into the material due to the fact that the ablation-resistant material has a low heat conductivity coefficient. Under the impact of high-temperature heat flow, the filler and/or the polymer can form a carbon layer on the surface of the material, so that heat can be prevented from invading the internal structure, and the internal structure is protected thermally.
The ablation resistant material includes resinous materials such as phenolic resins and the like. The phenolic resin is widely used for fiber reinforced composite materials due to the simple forming process, good heat resistance and high mechanical strength. Meanwhile, because the phenolic resin has outstanding instantaneous high-temperature ablation resistance, the phenolic resin is often used as a matrix of an ablation-resistant composite material. The American NASA is a Phencarb series light carbonized type ablative material prepared by taking phenolic resin as a matrix, the surface ablation rate is low, and the carbon layer after ablation is thick. The phenolic impregnated carbon ablation material (PICA) prepared by taking phenolic resin as a matrix by the American AMES center is successfully applied to a star dust number reentry module thermal protection system, and the PICA material is also adopted as the thermal protection material of a new American generation manned spacecraft Hunter seat.
Although the traditional phenolic resin has certain high-temperature ablation resistance and high material strength, the phenolic resin is suitable for preparing ablation-resistant materials. However, the elongation at break is low, a glassy structure is formed after carbonization, a carbonized product is difficult to graphitize, the graphitization degree of combined carbon is low, so that the oxidation resistance is poor, a uniform structure is formed after carbonization, the crack propagation resistance is poor, the problem that a carbon layer is degraded in the flight process may occur, and the like, so that the material is difficult to meet the new requirements of the survivability and maneuverability of an aircraft in the future.
The mesophase pitch (mesophase pitch) is a mixture composed of a plurality of flat disc-shaped polycyclic aromatic hydrocarbons with the relative molecular mass of 370-2000; has the advantages of high carbon residue rate, high density, easy graphitization and the like. Mesophase pitch is commonly used to prepare materials such as high thermal conductivity carbon fibers. In addition, the intermediate phase asphalt modified phenolic resin is selected in the literature 'development of intermediate phase asphalt-phenolic resin bonding agent for magnesia carbon bricks' (Zhang Xue Song et al, refractory material, 2007, 41(4):271 and 273.), so that the carbon residue rate is improved; the literature selects phenolic resin with carbon residue rate obviously lower than that of the mesophase pitch, and the mesophase pitch is added into the phenolic resin to improve the carbon residue rate of the mesophase pitch-phenolic resin compound. The literature focuses on the change of the overall carbon residue rate after the mesophase pitch and the phenolic resin are compounded, and the problem that the carbon residue rate of the traditional phenolic resin is not high is expected to be overcome, so that the product can be applied to the magnesia carbon brick adhesive industry. However, the method is only suitable for improving the carbon residue rate of the phenolic resin with the carbon residue rate obviously lower than that of the mesophase pitch, and is not suitable for the phenolic resin with high carbon residue rate; the problems of improving the strength of the overall carbon layer of the ablated phenolic resin and improving the anti-scouring performance of the overall carbon layer are not solved.
Therefore, further research and exploration are urgently needed for mesophase pitch and phenolic resin to research and develop a modified phenolic resin material with excellent ablation resistance and excellent scouring resistance so as to meet the application in severe environments such as high-temperature gas and pneumatic heat flow scouring.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a mesophase pitch modified ablation-resistant resin matrix material, a preparation method and application thereof.
The invention provides a mesophase pitch modified ablation-resistant resin matrix material, which is prepared from the following raw materials in parts by weight: 100-120 parts of ablation-resistant resin and 1-200 parts of mesophase pitch.
Further, the ablation-resistant resin matrix material is prepared from the following raw materials in parts by weight: 120 parts of ablation-resistant resin and 6-30 parts of mesophase pitch.
Further, the ablation-resistant resin matrix material is prepared from the following raw materials in parts by weight: 120 parts of ablation-resistant resin and 30 parts of mesophase pitch.
Further, the ablation-resistant resin is phenolic resin, bismaleimide resin, polyimide resin, phthalonitrile resin, benzoxazine resin, aryne resin, cyanate resin or modified epoxy resin;
and/or the mesophase pitch is naphthalene mesophase pitch;
preferably, the ablation-resistant resin is a phenolic resin;
more preferably, the phenolic resin is a borophenolic resin.
Furthermore, the ablation-resistant resin matrix material is obtained by mixing ablation-resistant resin and mesophase pitch, and then carrying out hot-pressing curing molding;
preferably, the mixing mode is powder mixing;
and/or, the hot-pressing curing molding process is to keep the temperature at 100-120 ℃ for 30-120 min, heat the temperature from 100-120 ℃ to 140-150 ℃ and then keep the temperature for 30-120 min, then heat the temperature from 140-150 ℃ to 180 ℃ and keep the temperature for 1-2 h, and finally heat the temperature from 180 ℃ to 200 ℃ and keep the temperature for 1-2 h.
Further, the air conditioner is provided with a fan,
the curing process comprises the following steps: keeping the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃, keeping the temperature for 30min, heating from 140 ℃ to 180 ℃, keeping the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and keeping the temperature for 1 h;
preferably, the rate of each temperature rise is 5-20 ℃/min;
and/or, normal pressure at 110 ℃; and/or the pressure is 12-15 MPa when the temperature is raised to 140-200 ℃.
The invention also provides a preparation method of the ablation-resistant resin matrix material, which comprises the following steps:
(1) crushing ablation-resistant resin and intermediate phase asphalt, weighing the ablation-resistant resin and the intermediate phase asphalt according to the weight ratio, and mixing the ablation-resistant resin and the intermediate phase asphalt to obtain mixed powder;
(2) hot-pressing, solidifying and molding the mixed powder, and cooling to obtain the powder;
preferably, the first and second electrodes are formed of a metal,
the hot-pressing curing molding process comprises the steps of keeping the temperature of 100-120 ℃ for 30-120 min, heating the temperature of 100-120 ℃ to 140-150 ℃, keeping the temperature for 30-120 min, heating the temperature of 140-150 ℃ to 180 ℃, keeping the temperature for 1-2 h, heating the temperature of 180 ℃ to 200 ℃ and keeping the temperature for 1-2 h.
Further, the curing process comprises the following steps: keeping the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃, keeping the temperature for 30min, heating from 140 ℃ to 180 ℃, keeping the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and keeping the temperature for 1 h;
preferably, the rate of each temperature rise is 5-20 ℃/min;
and/or, normal pressure at 110 ℃; and/or the pressure is 12-15 MPa when the temperature is raised to 140-200 ℃.
The invention also provides the application of the ablation-resistant resin matrix material in preparing materials and parts with ablation resistance requirements;
preferably, the use of the ablation-resistant resin matrix material in the preparation of an ablation heat-protective composite;
more preferably, the use of said ablation-resistant resin matrix material for the preparation of materials for the protection and sealing of structures and components in aircraft and related equipment which are subjected to high temperature combustion gases and aerodynamic heat flows which are subjected to the harsh environment.
The ablation-resistant resin matrix material prepared by the invention can be used as a base material, and is reinforced and modified by a reinforcing material to obtain a composite material, and the composite material can keep the excellent ablation resistance and erosion resistance of the ablation-resistant resin matrix material.
Therefore, the invention also provides a composite material which is prepared by the reinforcing material and the ablation-resistant resin matrix material;
preferably, the reinforcement material is a fiber and the composite material is a fiber-reinforced ablation-resistant composite material.
The invention prepares an intermediate phase asphalt modified ablation-resistant resin matrix material, combines the liquid carbonization process of intermediate phase asphalt with the solid carbonization process of a three-dimensional resin cross-linked network in the ablation process, introduces an intermediate phase asphalt liquid crystal ordered carbon structure into a carbon layer, reduces the generation of shrinkage cracks in the carbon layer, increases the graphitization degree of the carbon layer, obviously improves the erosion resistance of the material under the condition of high heat flow and oxygen enrichment, ensures that the formed carbon layer is more complete and compact, and further obviously improves the ablation resistance of the material. The ablation-resistant resin matrix material is suitable for preparing resin-based ablation heat-proof composite materials, and can be applied to the preparation of heat-proof structures of related equipment such as high-speed aircrafts, engines and the like so as to protect structures and parts which need to withstand severe environments such as high-temperature gas or pneumatic heat flow scouring and the like.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
Figure 1 is a graph showing the results of the line ablation rate for various groups of phenolic resin ablation-resistant materials.
FIG. 2 is a macroscopic view of the surface of groups of phenolic resin ablation-resistant materials after ablation for different periods of time.
FIG. 3 shows MPBPR of a phenolic resin ablation-resistant material20Macro-map of surface after ablation for 5s and XRD and infrared results of different parts of surface after ablation: a is a surface macroscopic view; b is an XRD spectrum; and c is an infrared spectrum.
Fig. 4 is an SEM picture of the carbon layer cross-section after ablation of various groups of phenolic resin ablation-resistant materials: a-c are SEM pictures of BPR under different magnification; d-f is MPBPR5SEM pictures at different magnifications; g-i is MPBPR10SEM pictures at different magnifications; j-l is MPBPR20Under different magnificationSEM pictures of (d).
FIG. 5 is MPBPR20Surface SEM images after different times of ablation.
FIG. 6 shows MPBPR made of an ablation-resistant phenolic resin material20SEM pictures of intermediate states of spherical structure formation in the carbon layer during ablation.
FIG. 7 shows XRD and Raman characterization results of the central carbon layer of BPR and MPBPR composites after 4WM ablation: a is an XRD characterization result; and b is a Raman characterization result.
FIG. 8 is an air atmosphere thermogravimetric analysis of the central carbon layer of BPR and MPBPR composites after 4WM ablation.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
Phenolic resin: the THC-400 boron phenolic resin has the gel speed of 70-100 s/200 ℃, the free phenol content of less than 7 percent and is yellow block-shaped. The char yield thereof was 74.2%.
Mesophase pitch: naphthalene mesophase pitch (mesophase content 100%) produced by mitsubishi gas chemical corporation of japan. The carbon residue rate was 72.5%.
Example 1 preparation of ablation resistant Material of phenolic resin of the invention
Respectively crushing the phenolic resin (BPR) and the Mesophase Pitch (MP) in a high-speed crushing mixer, and sieving to obtain powder of 800 meshes to 1200 meshes. 120g of the sieved phenolic resin and 6g of the mesophase pitch are mixed in a high-speed crushing mixer for more than half an hour to obtain mixed powder. And (3) putting the prepared mixed powder into a hot-pressing die for mould pressing, curing and forming. And (3) a curing process: keeping at 110 deg.C for 30min without pressurizing; heating from 110 ℃ to 140 ℃, wherein the heating rate is 5 ℃/min; preserving the heat at 140 ℃ for 30min, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 180 ℃ for 2h, and keeping the pressure at 12-15 MPa; heating from 180 ℃ to 200 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 200 ℃ for 1h, and keeping the pressure at 12-15 MPa; finally, keeping the pressure at 12-15 MPa, and naturally cooling to room temperature to obtain the mesophase pitch modified phenolAldehyde resin ablation-resistant material named MPBPR5(M5)。
Example 2 preparation of ablation resistant Material of phenolic resin of the invention
Respectively crushing the phenolic resin (BPR) and the Mesophase Pitch (MP) in a high-speed crushing mixer, and sieving to obtain powder of 800 meshes to 1200 meshes. 120g of the sieved phenolic resin and 12g of the mesophase pitch are mixed in a high-speed crushing mixer for more than half an hour to obtain mixed powder. And (3) putting the prepared mixed powder into a hot-pressing die for mould pressing, curing and forming. And (3) a curing process: keeping at 110 deg.C for 30min without pressurizing; heating from 110 ℃ to 140 ℃, wherein the heating rate is 5 ℃/min; preserving the heat at 140 ℃ for 30min, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 180 ℃ for 2h, and keeping the pressure at 12-15 MPa; heating from 180 ℃ to 200 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 200 ℃ for 1h, and keeping the pressure at 12-15 MPa; and finally, keeping the pressure at 12-15 MPa, and naturally cooling to room temperature to obtain the mesophase pitch modified phenolic resin ablation-resistant material named MPBPR10(M10)。
Example 3 preparation of ablation resistant Material of phenolic resin of the invention
Respectively crushing the phenolic resin (BPR) and the Mesophase Pitch (MP) in a high-speed crushing mixer, and sieving to obtain powder of 800 meshes to 1200 meshes. 120g of the sieved phenolic resin and 30g of the mesophase pitch are mixed in a high-speed crushing mixer for more than half an hour to obtain mixed powder. And (3) putting the prepared mixed powder into a hot-pressing die for mould pressing, curing and forming. And (3) a curing process: keeping at 110 deg.C for 30min without pressurizing; heating from 110 ℃ to 140 ℃, wherein the heating rate is 5 ℃/min; preserving the heat at 140 ℃ for 30min, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 180 ℃ for 2h, and keeping the pressure at 12-15 MPa; heating from 180 ℃ to 200 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 200 ℃ for 1h, and keeping the pressure at 12-15 MPa; and finally, keeping the pressure at 12-15 MPa, and naturally cooling to room temperature to obtain the mesophase pitch modified phenolic resin ablation-resistant material named MPBPR20(M20)。
Comparative example 1 preparation of other phenolic resin ablation resistant materials
The phenolic resin (BPR) is crushed in a high-speed crushing mixer and sieved, and 800 meshes to 1200 meshes of powder is obtained. And (3) putting 120g of sieved phenolic resin powder into a hot-pressing die for die pressing, curing and forming. And (3) a curing process: keeping at 110 deg.C for 30min without pressurizing; heating from 110 ℃ to 140 ℃, wherein the heating rate is 5 ℃/min; preserving the heat at 140 ℃ for 30min, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 180 ℃ for 2h, and keeping the pressure at 12-15 MPa; heating from 180 ℃ to 200 ℃, wherein the heating rate is 5 ℃/min, and the pressure is kept at 12-15 MPa; keeping the temperature at 200 ℃ for 1h, and keeping the pressure at 12-15 MPa; and finally, keeping the pressure at 12-15 MPa, and naturally cooling to room temperature to obtain the phenolic resin ablation-resistant material named BPR.
Comparative example 2 preparation of other phenolic resin ablation-resistant Material
Respectively crushing the phenolic resin (BPR) and the Mesophase Pitch (MP) in a high-speed crushing mixer, and sieving to obtain powder of 800 meshes to 1200 meshes. 120g of the sieved phenolic resin and 30g of the mesophase pitch are mixed in a high-speed crushing mixer for more than half an hour to obtain mixed powder. And (3) putting the prepared mixed powder into a hot-pressing die for mould pressing, curing and forming. And (3) a curing process: keeping at 150 deg.C for 30min under 12 MPa; then heating from 150 ℃ to 180 ℃, wherein the heating rate is 5 ℃/min, the temperature is kept at 180 ℃ for 2h, and the pressure is 12 MPa; then the temperature is increased from 180 ℃ to 200 ℃, the heating rate is 5 ℃/min, the temperature is kept at 200 ℃ for 1h, and the pressure is 12 MPa. And finally, keeping the pressure at 12MPa, and naturally cooling to room temperature to obtain the other mesophase pitch modified phenolic resin ablation-resistant material. Compared with the embodiment 3, the composite material prepared by the process has obviously poorer performances such as ablation resistance, scouring resistance and the like.
The advantageous effects of the present invention are demonstrated by specific test examples below.
Test example 1 test of ablation Properties of mesophase pitch-modified phenol resin ablation resistant Material
1. Test method
The ablation resistance detection is carried out by adopting the phenolic resin ablation-resistant materials prepared in the examples 1-3 and the comparative example 1 according to the following test method:
ablation performance test criteria: GJB 323A-1996; heat flux density: 4100kW/m2(ii) a Ablation time: for 30 s.
2. Test results
For materials with stringent requirements for maintaining aerodynamic profiles, the rate of wire ablation is clearly the most important indicator. The present invention examined the line ablation rate of each group of phenolic resin ablation-resistant materials, and the results are shown in fig. 1. As can be seen from fig. 1: when the flame is ablated for 5-10 s by oxyacetylene, the ablation expansion phenomenon occurs to both BPR and MPBPR, and the ablation expansion phenomenon is slightly improved by introducing MP compared with a pure sample. The ablation behavior of the material is changed from ablation expansion to ablation retreat after ablation for 10-30 s, the ablation retreat phenomenon of the material can be obviously weakened by introducing MP into the phenolic resin matrix, the linear ablation rate of the material is obviously reduced, and the ablation dimensional (shape maintaining) capability is greatly improved. Therefore, the ablation resistance of the mesophase pitch modified phenolic resin ablation-resistant material is obviously improved.
FIG. 2 shows the surface macro-topography of 5s, 10s, 20s and 30s ablated by the phenolic resin ablation-resistant materials in each group. Obvious cracks appear on the surface after the BPR is ablated for 10s, and the large size of the gaps among the carbon blocks enables oxygen under the condition of high heat flow and oxygen enrichment to easily penetrate through the ablated surface of the material to erode the interior of the material. And 5 parts of MP (MPBPR)5) 10 parts of (MPBPR)10) In this case, the ablated surface was required to be flushed with an oxyacetylene flame for 20s and 30s before significant cracking occurred. After addition of 20 parts of MP (MPBPR)20) After 30s of ablation, almost no significant voids were observed at the ablated surface. The introduction of MP leads the carbon layer on the surface of the ablated material to be more compact, and oxygen is isolated outside the ablated surface of the material to a great extent, which is helpful for improving the ablation resistance of the material.
FIG. 3 shows MPBPR of a phenolic resin ablation-resistant material20And (4) researching the composition structure of different areas of the carbon layer after ablation. Fig. 3a is a photomicrograph of the surface after ablation for 5s with 20 parts mesophase pitch added, and fig. 3b and 3c are XRD and infrared characterization of different areas of its carbon layer. MPBPR20Ablating the center and edge of the surfaceThe colors were very different and by observing the topography of the ablated surface as shown in figure 2, it was found that as the amount of MP added was increased and the ablation time was decreased, the black edge portions of the ablated surface of the composite increased. XRD and infrared spectrum show that the charring degree of the central part of the ablation is higher than that of the edge part. B is not basically observed on the XRD spectrogram of the central carbon layer2O3While the edge carbon layer observed significant B2O3A peak indicating that the black border portion is subjected to a lower temperature than the center, B2O3And has not been volatilized. In conclusion, the addition of MP can effectively inhibit the heat from diffusing from the oxyacetylene ablation center to the periphery.
Figure 4 is an SEM image of the cross-section of the carbon layer after ablation of each set of phenolic resin ablation-resistant materials. The surface of the carbon layer is smooth and compact after the ablation material is ablated, and the defects are fewer. Therefore, the erosion of the internal resin matrix by oxygen through the pyrolysis path is effectively suppressed. In addition, due to the liquid phase carbonization process of pitch in the ablation process and the surface tension of pitch in the process, spherical structures are uniformly distributed in the carbon layer, so that the pores and cracks in the phenolic pyrolytic carbon are effectively filled, and the diameter of the spherical structures in the carbon is gradually increased along with the increase of the content of pitch. Therefore, the introduction of MP can form a spherical nano structure on the phenolic resin amorphous carbon through in-situ liquid phase carbonization in the ablation carbonization process of the material, effectively fills the gap defect, isolates the invasion of oxygen to the inside in an oxygen-rich high-heat-flow environment on one hand, and increases the structural strength of a material carbon layer on the other hand, so that the ablation resistance of the material is obviously improved.
FIG. 5 shows MPBPR made of an ablation-resistant phenolic resin material20SEM pictures of carbon layer cross-sections after ablation at different ablation times. Spherical nanostructures are distributed in the carbon layer after ablation for 5s, 10s and 20 s. With the continuous ablation of oxyacetylene, the spherical structures are gradually increased and fill the gaps and cracks in the carbon layer. It can be observed that after 5s of ablation, large-area naked void defects exist in the material carbon layer, and the distribution of the spherical nano structures is not continuous. After ablation for 10s, the spherical nano-structure in the carbon layer is distributed more continuously, and the carbon layer has the effect of a phenolic resin carbon layerCertain repairing and reinforcing effects. After ablation is carried out for 20s, the surface of the carbon layer is completely covered by the spherical nano structure, and gaps generated by pyrolysis in the phenolic resin carbon and shrinkage cracks generated by a carbon forming process are also filled and repaired to a certain extent.
FIG. 6 shows an MPBPR of the mesophase pitch-modified phenolic resin ablation-resistant material of the present invention20SEM pictures of intermediate states of spherical structure formation in the carbon layer during ablation. As shown, it is clearly observed that the intermediate state in the process of forming the spherical structure is fixed due to the stopping of the oxyacetylene flame. The prism walls of the mesosphere nano structure are in lamellar strip-shaped structures, which are consistent with the structure of mesophase pitch liquid crystal ordered carbon. This demonstrates that the spherical nanostructures formed during ablation are due to the liquid phase carbonization process of pitch during ablation.
FIG. 7 shows XRD and Raman characterization results of the central carbon layer of BPR and MPBPR composites after 4WM ablation. In order to verify whether the introduction of MP can promote the graphitization of the carbon layer, the carbon of the ablation center which is directly contacted with oxyacetylene flame is collected by an XRD (X-ray diffraction) and Raman spectrum analysis method. As shown in fig. 7, the XRD patterns of both pure BPR and MPBPR composites had two peaks corresponding to (002) and (101). The peak appearing around 26.0 ° is the (002) peak, corresponding to a near graphitic structure, with the peak width narrowing as the intensity of the peak increases with increasing MP content (0 wt.%, 5 wt.%, 10 wt.%, 20 wt.%). With the addition of MP, d002 gradually decreases, and Lc gradually increases, indicating that the graphitization degree of the sample is higher. The results of Raman spectroscopy on all samples showed peaks at 1360 and 1580cm-1Two peaks appear nearby, corresponding to the D and G bands, respectively. The intensity ratio (ID/IG) of the D band and the G band can be used as an index reflecting the degree of carbon disorder. Lower ID/IG ratios were observed in samples of MPBPR composites, indicating that graphitization of the composites was promoted. In conclusion, the mesophase pitch can form a carbonized structure with higher graphitization degree in the liquid carbonization process, and is beneficial to improving the oxidation resistance and the structural toughness of the ablation-resistant phenolic resin material.
FIG. 8 is an air atmosphere thermogravimetric analysis of the central carbon layer of BPR and MPBPR composites after 4WM ablation. As shown in fig. 8, thermogravimetry of the carbon layer after ablation of the mesophase pitch-modified phenolic resin composite material shows that the mesophase pitch-modified carbon layer has better oxidation resistance in an air atmosphere. Therefore, the introduction of the mesophase pitch ordered carbon ensures that the carbon layer is more stable in the ablation process, better protects the resin matrix from being eroded by external oxygen-rich heat flow, and obviously improves the anti-scouring performance of the resin matrix under the condition of high heat flow and oxygen-rich.
In conclusion, the ablation-resistant resin matrix material modified by the mesophase pitch is prepared, the liquid carbonization process of the mesophase pitch and the solid carbonization process of the three-dimensional resin cross-linked network are combined in the ablation process, the mesophase pitch liquid crystal ordered carbon structure is introduced into the carbon layer, the generation of shrinkage cracks in the carbon layer is reduced, the graphitization degree of the carbon layer is increased, the scouring resistance of the material under the condition of high heat flow and oxygen enrichment is obviously improved, the formed carbon layer is more complete and compact, and the ablation resistance of the material is obviously improved. The ablation-resistant resin matrix material is suitable for preparing resin-based ablation heat-proof composite materials, and can be applied to the preparation of heat-proof structures of related equipment such as high-speed aircrafts, engines and the like so as to protect structures and parts which need to withstand severe environments such as high-temperature gas or pneumatic heat flow scouring and the like.
Claims (10)
1. An ablation-resistant resin matrix material modified by mesophase pitch, which is characterized in that: the composition is prepared from the following raw materials in parts by weight: 100-120 parts of ablation-resistant resin and 1-200 parts of mesophase pitch.
2. The ablation-resistant resin base material according to claim 1, characterized in that: the composition is prepared from the following raw materials in parts by weight: 120 parts of ablation-resistant resin and 6-30 parts of mesophase pitch.
3. The ablation-resistant resin base material according to claim 2, characterized in that: the composition is prepared from the following raw materials in parts by weight: 120 parts of ablation-resistant resin and 30 parts of mesophase pitch.
4. The ablation-resistant resin base material according to any one of claims 1 to 3, wherein: the ablation-resistant resin is phenolic resin, bismaleimide resin, polyimide resin, phthalonitrile resin, benzoxazine resin, aryne resin, cyanate ester resin or modified epoxy resin;
and/or the mesophase pitch is naphthalene mesophase pitch;
preferably, the ablation-resistant resin is a phenolic resin;
more preferably, the phenolic resin is a borophenolic resin.
5. The ablation-resistant resin base material according to any one of claims 1 to 3, wherein: the ablation-resistant resin matrix material is obtained by mixing ablation-resistant resin and mesophase pitch, and then carrying out hot-pressing curing molding;
preferably, the mixing mode is powder mixing;
and/or, the hot-pressing curing molding process is to keep the temperature at 100-120 ℃ for 30-120 min, heat the temperature from 100-120 ℃ to 140-150 ℃ and then keep the temperature for 30-120 min, then heat the temperature from 140-150 ℃ to 180 ℃ and keep the temperature for 1-2 h, and finally heat the temperature from 180 ℃ to 200 ℃ and keep the temperature for 1-2 h.
6. The ablation-resistant resin base material according to claim 5, characterized in that:
the curing process comprises the following steps: keeping the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃, keeping the temperature for 30min, heating from 140 ℃ to 180 ℃, keeping the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and keeping the temperature for 1 h;
preferably, the rate of each temperature rise is 5-20 ℃/min;
and/or, normal pressure at 110 ℃; and/or the pressure is 12-15 MPa when the temperature is raised to 140-200 ℃.
7. The method for producing an ablation-resistant resin base material according to any one of claims 1 to 6, characterized in that: it comprises the following steps:
(1) crushing ablation-resistant resin and intermediate phase asphalt, weighing the ablation-resistant resin and the intermediate phase asphalt according to the weight ratio, and mixing the ablation-resistant resin and the intermediate phase asphalt to obtain mixed powder;
(2) hot-pressing, solidifying and molding the mixed powder, and cooling to obtain the powder;
preferably, the first and second electrodes are formed of a metal,
the hot-pressing curing molding process comprises the steps of keeping the temperature of 100-120 ℃ for 30-120 min, heating the temperature of 100-120 ℃ to 140-150 ℃, keeping the temperature for 30-120 min, heating the temperature of 140-150 ℃ to 180 ℃, keeping the temperature for 1-2 h, heating the temperature of 180 ℃ to 200 ℃ and keeping the temperature for 1-2 h.
8. The method of claim 7, wherein: the curing process comprises the following steps: keeping the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃, keeping the temperature for 30min, heating from 140 ℃ to 180 ℃, keeping the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and keeping the temperature for 1 h;
preferably, the rate of each temperature rise is 5-20 ℃/min;
and/or, normal pressure at 110 ℃; and/or the pressure is 12-15 MPa when the temperature is raised to 140-200 ℃.
9. Use of the ablation-resistant resin matrix material of any one of claims 1 to 6 in the preparation of materials and articles with ablation resistance requirements;
preferably, the use of the ablation-resistant resin matrix material in the preparation of an ablation heat-protective composite;
more preferably, the use of said ablation-resistant resin matrix material for the preparation of materials for the protection and sealing of structures and components in aircraft and related equipment which are subjected to high temperature combustion gases and aerodynamic heat flows which are subjected to the harsh environment.
10. A composite material characterized by: the composite material is made of a reinforcing material and the ablation-resistant resin matrix material of any one of claims 1 to 6;
preferably, the reinforcement material is a fiber and the composite material is a fiber-reinforced ablation-resistant composite material.
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