CN113845746B - Mesophase pitch modified ablation-resistant resin matrix material, and preparation method and application thereof - Google Patents
Mesophase pitch modified ablation-resistant resin matrix material, and preparation method and application thereof Download PDFInfo
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- 238000002679 ablation Methods 0.000 title claims abstract description 149
- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 69
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- 239000011159 matrix material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 38
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- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000009991 scouring Methods 0.000 claims abstract description 11
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- 239000002737 fuel gas Substances 0.000 claims abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 67
- 239000005011 phenolic resin Substances 0.000 claims description 59
- 229920001568 phenolic resin Polymers 0.000 claims description 59
- 238000010438 heat treatment Methods 0.000 claims description 44
- 238000001723 curing Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000010426 asphalt Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 2
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 65
- 229910052799 carbon Inorganic materials 0.000 abstract description 53
- 238000003763 carbonization Methods 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000005087 graphitization Methods 0.000 abstract description 9
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000011010 flushing procedure Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 7
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
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- 238000012876 topography Methods 0.000 description 2
- 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 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101001133654 Homo sapiens Protein PALS1 Proteins 0.000 description 1
- 102100034054 Protein PALS1 Human genes 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000011819 refractory material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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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
-
- 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 & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a mesophase pitch modified ablation-resistant resin matrix material, a preparation method and application thereof, and belongs to the technical field of ablation-resistant materials. The composite material 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. According to the material, the liquid carbonization process of the mesophase pitch is combined with the solid carbonization process of the resin three-dimensional crosslinked network in the ablation process, and a 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 material is increased, the anti-scouring performance of the material under the high-heat-flow oxygen-enriched condition is remarkably improved, the formed carbon layer is more complete and compact, and the ablation resistance of the material is remarkably improved. The material is suitable for preparing resin-based ablation heat-resistant composite materials, and can be applied to preparing heat-resistant structures of related equipment such as high-speed aircrafts, engines and the like so as to protect structures and components which need to withstand severe environments such as high-temperature fuel gas or pneumatic heat flow flushing.
Description
Technical Field
The invention belongs to the technical field of ablation-resistant materials, and particularly relates to a mesophase pitch modified ablation-resistant resin matrix material, and a preparation method and application thereof.
Background
Because the service environment of aerospace equipment such as aircrafts is extremely bad, the heat-resistant layer has very high requirements on ablation resistance, hot-flow scouring resistance, mechanical properties and the like. The ablation-resistant mechanism of the heat-resistant layer is that after the ablation-resistant material is heated, heat is difficult to conduct into the material due to the fact that the heat-resistant material has 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 thermally protected.
The ablation resistant material includes a resin-based material such as a phenolic resin or the like. Phenolic resin is widely used for fiber reinforced composite materials due to its simple molding process, good heat resistance and high mechanical strength. Meanwhile, phenolic resin has outstanding instantaneous high-temperature ablation resistance and is often used as a matrix of the ablation-resistant composite material. PhenCarb series light charring type ablative materials prepared by taking phenolic resin as a matrix in NASA in the United states have low surface ablative rate and the thickness of the ablated carbon layer. Phenolic impregnated carbon ablative materials (PICA) prepared by taking phenolic resin as a matrix in the center of Ames, which are successfully applied to a star dust return cabin heat protection system, are also used as heat protection materials of PICA materials in the new generation of manned spacecraft 'hunter seats' in the United states.
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 fracture elongation is low, a glassy structure is formed after carbonization, the carbonized product is difficult to graphitize, the graphitization degree of the combined carbon is low, oxidation resistance is poor, and a uniform structure is formed after carbonization, so that the crack propagation resistance is poor, the problems of carbon layer degradation and the like can possibly occur in the flying process, and the material is difficult to meet new requirements of future on the survival capability and the maneuverability of an aircraft.
Mesophase pitch (mesophase pitch) is a mixture composed of a plurality of flat-disk-shaped polycyclic aromatic hydrocarbons with relative molecular mass of 370-2000; has the advantages of high carbon residue rate, high density, easy graphitization, etc. Mesophase pitch is often used to prepare materials such as high thermal conductivity carbon fibers. In addition, the literature (development of mesophase pitch-phenolic resin binders for magnesia carbon bricks) (Zhang Xuesong, etc., refractory materials, 2007, 41 (4): 271-273.) chooses mesophase pitch-modified phenolic resin to increase the carbon residue rate; the literature selects phenolic resin with carbon residue rate obviously lower than that of intermediate phase pitch, and the intermediate phase pitch is added into the phenolic resin to improve the carbon residue rate of the intermediate phase pitch-phenolic resin compound. The literature focuses on the change of the overall carbon residue after the intermediate phase asphalt and the phenolic resin are compounded, and hopefully can improve the defect of low carbon residue of the traditional phenolic resin, so that the product can be applied to the magnesia carbon brick adhesive industry. But the method is only suitable for improving the residual carbon rate of the phenolic resin with the residual carbon rate obviously lower than that of the mesophase pitch, and is not suitable for the phenolic resin with high residual carbon rate; the problem of improving the strength of the whole carbon layer of the ablated phenolic resin and the anti-scouring performance of the phenolic resin is not solved.
Therefore, further research and exploration are urgently needed for the mesophase pitch and phenolic resin to develop a modified phenolic resin material with excellent ablation resistance and excellent anti-scouring performance so as to meet the application under severe environments such as high-temperature fuel gas, pneumatic heat flow scouring and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an ablation-resistant resin matrix material modified by mesophase pitch, and 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 boron phenolic resin.
Further, the ablation-resistant resin matrix material is obtained by mixing ablation-resistant resin and mesophase pitch, and then performing hot pressing, curing and molding;
preferably, the mixing means is powder mixing;
and/or the hot press solidification molding process is to heat-preserving for 30-120 min at 100-120 ℃, heat-preserving for 30-120 min after heating from 100-120 ℃ to 140-150 ℃, heat-preserving for 1-2 h after heating from 140-150 ℃ to 180 ℃, and heat-preserving for 1-2 h after heating from 180 ℃ to 200 ℃.
Further, the method comprises the steps of,
the curing process comprises the following steps: maintaining the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃ and then maintaining the temperature for 30min, heating from 140 ℃ to 180 ℃ and then maintaining the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and then maintaining the temperature for 1h;
preferably, the rate of each heating is 5-20 ℃/min;
and/or, at 110 ℃ is normal pressure; 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 the ablation-resistant resin and the mesophase pitch, weighing the ablation-resistant resin and the mesophase pitch according to the weight ratio, and mixing the ablation-resistant resin and the mesophase pitch to obtain mixed powder;
(2) Hot-pressing, solidifying and molding the mixed powder, and cooling to obtain the product;
preferably, the method comprises the steps of,
the hot press curing molding process is that the temperature is kept for 30-120 min at 100-120 ℃, the temperature is kept for 30-120 min after the temperature is raised from 100-120 ℃ to 140-150 ℃, then the temperature is kept for 1-2 h after the temperature is raised from 140-150 ℃ to 180 ℃, and finally the temperature is kept for 1-2 h after the temperature is raised from 180 ℃ to 200 ℃.
Further, the curing process comprises the following steps: maintaining the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃ and then maintaining the temperature for 30min, heating from 140 ℃ to 180 ℃ and then maintaining the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and then maintaining the temperature for 1h;
preferably, the rate of each heating is 5-20 ℃/min;
and/or, at 110 ℃ is normal pressure; 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 a material with the ablation-resistant performance requirement and a workpiece;
preferably, the use of the ablation resistant resin matrix material in the preparation of an ablation heat resistant composite;
more preferably, the use of the ablation resistant resin matrix material in the manufacture of materials for the protection and sealing of structures and components that are subjected to high temperature combustion gases and aerodynamic heat flow scouring harsh environments in aircraft and related equipment devices.
The ablation-resistant resin matrix material prepared by the invention can be used as a base material, and is reinforced and modified by using a reinforcing material to obtain a composite material, and the composite material can keep the excellent ablation resistance and the excellent anti-scouring performance of the ablation-resistant resin matrix material.
Therefore, the invention also provides a composite material which is made of the reinforcing material and the ablation-resistant resin matrix material;
preferably, the reinforcing material is a fibre and the composite material is a fibre reinforced ablation resistant composite material.
According to the invention, the liquid carbonization process of the mesophase pitch is combined with the solid carbonization process of the resin three-dimensional cross-linked network in the ablation process, and a 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 is increased, the anti-scouring performance of the material under the high-heat-flow oxygen-enriched condition is remarkably improved, the formed carbon layer is more complete and compact, and the ablation resistance of the material is remarkably improved. The ablation-resistant resin matrix material is suitable for preparing resin-based ablation heat-resistant composite materials, and can be applied to preparing heat-resistant structures of related equipment such as high-speed aircrafts, engines and the like so as to protect structures and components which need to withstand severe environments such as high-temperature gas or pneumatic heat flow flushing.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a graph showing the results of the line ablation rate for each set of phenolic resin ablation resistant materials.
FIG. 2 is a macroscopic view of the surface of each set of phenolic resin ablation resistant materials after different times of ablation.
FIG. 3 shows an MPBPR of a phenolic resin ablation resistant material 20 Macroscopic view of the surface after 5s ablation and XRD and infrared results of different parts of the surface after ablation: a is a surface macroscopic view; b is XRD pattern; and c is an infrared spectrum.
Fig. 4 is an SEM photograph of a cross-section of a carbon layer after ablation of each set of phenolic resin ablation resistant materials: a-c are SEM pictures of BPR at different magnifications; d-f is MPBPR 5 SEM pictures at different magnifications; g-i is MPBPR 10 SEM pictures at different magnifications; j-l is MPBPR 20 SEM pictures at different magnifications.
FIG. 5 is MPBPR 20 SEM images of the surface after ablation for various times.
FIG. 6 shows a phenolic resin ablation resistant material MPBPR 20 SEM 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 the BPR and MPBPR composites after 4WM ablation: a is XRD characterization result; b is the raman characterization result.
FIG. 8 is an air atmosphere thermogravimetric analysis of a center carbon layer after 4WM ablation of a BPR and MPBPR composite.
Detailed Description
The materials and equipment used in the embodiments of the present invention are all known products and are 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 yellow blocky shape. The carbon residue rate is 74.2%.
Mesophase pitch: naphthalene based mesophase pitch (mesophase content 100%) produced by mitsubishi gas chemistry company of japan. The carbon residue rate is 72.5%.
EXAMPLE 1 preparation of the phenolic resin ablation-resistant Material of the invention
Pulverizing phenolic resin (BPR) and Mesophase Pitch (MP) in a high-speed pulverizing mixer, sieving, and collecting 800-1200 mesh powder. 120g of the screened 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 filling the prepared mixed powder into a hot-pressing die for compression molding, curing and forming. The curing process comprises the following steps: not pressurizing at 110 ℃ and keeping for 30min; heating from 110 ℃ to 140 ℃ at a heating rate of 5 ℃/min; preserving heat for 30min at 140 ℃, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, heating at a speed of 5 ℃/min, and keeping the pressure at 12-15 MPa; preserving heat for 2h at 180 ℃ 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; preserving heat for 1h at 200 ℃ and keeping the pressure at 12-15 MPa; finally, maintaining the pressure at 12-15 MPa, naturally cooling to room temperature to obtain the mesophase pitch modified phenolic resin ablation-resistant material named MPBPR 5 (M5)。
EXAMPLE 2 preparation of the phenolic resin ablation-resistant Material of the invention
Pulverizing phenolic resin (BPR) and Mesophase Pitch (MP) in a high-speed pulverizing mixer, sieving, and collecting 800-1200 mesh powder. 120g of the screened 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 filling the prepared mixed powder into a hot-pressing die for compression molding, curing and forming. The curing process comprises the following steps: not pressurizing at 110 ℃ and keeping for 30min; heating from 110 ℃ to 140 ℃ at a heating rate of 5 ℃/min;140 DEG CPreserving heat for 30min, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, heating at a speed of 5 ℃/min, and keeping the pressure at 12-15 MPa; preserving heat for 2h at 180 ℃ 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; preserving heat for 1h at 200 ℃ and keeping the pressure at 12-15 MPa; finally, maintaining the pressure at 12-15 MPa, naturally cooling to room temperature to obtain the mesophase pitch modified phenolic resin ablation-resistant material named MPBPR 10 (M10)。
EXAMPLE 3 preparation of the phenolic resin ablation-resistant Material of the invention
Pulverizing phenolic resin (BPR) and Mesophase Pitch (MP) in a high-speed pulverizing mixer, sieving, and collecting 800-1200 mesh powder. 120g of the screened 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 filling the prepared mixed powder into a hot-pressing die for compression molding, curing and forming. The curing process comprises the following steps: not pressurizing at 110 ℃ and keeping for 30min; heating from 110 ℃ to 140 ℃ at a heating rate of 5 ℃/min; preserving heat for 30min at 140 ℃, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, heating at a speed of 5 ℃/min, and keeping the pressure at 12-15 MPa; preserving heat for 2h at 180 ℃ 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; preserving heat for 1h at 200 ℃ and keeping the pressure at 12-15 MPa; finally, maintaining the pressure at 12-15 MPa, naturally cooling to room temperature to obtain the mesophase pitch modified phenolic resin ablation-resistant material named MPBPR 20 (M20)。
Comparative example 1 preparation of other phenolic resin ablation resistant Material
Pulverizing phenolic resin (BPR) in a high-speed pulverizing mixer, sieving, and collecting 800-1200 mesh powder. 120g of the sieved phenolic resin powder is put into a hot-pressing mold for compression molding, solidification and molding. The curing process comprises the following steps: not pressurizing at 110 ℃ and keeping for 30min; heating from 110 ℃ to 140 ℃ at a heating rate of 5 ℃/min; preserving heat for 30min at 140 ℃, and gradually pressurizing to 12-15 MPa; heating from 140 ℃ to 180 ℃, heating at a speed of 5 ℃/min, and keeping the pressure at 12-15 MPa; preserving heat for 2h at 180 ℃ 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; preserving heat for 1h at 200 ℃ and keeping the pressure at 12-15 MPa; and finally, maintaining 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
Pulverizing phenolic resin (BPR) and Mesophase Pitch (MP) in a high-speed pulverizing mixer, sieving, and collecting 800-1200 mesh powder. 120g of the screened 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 filling the prepared mixed powder into a hot-pressing die for compression molding, curing and forming. The curing process comprises the following steps: maintaining at 150deg.C for 30min under 12MPa; then heating from 150 ℃ to 180 ℃, keeping the temperature at 180 ℃ for 2 hours at a heating rate of 5 ℃/min and a pressure of 12MPa; 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 12MPa. And finally, maintaining the pressure at 12MPa, and naturally cooling to room temperature to obtain other mesophase pitch modified phenolic resin ablation-resistant materials. Compared with the embodiment 3, the composite material prepared by the process has significantly poorer ablation resistance, erosion resistance and other properties.
The beneficial effects of the present invention are demonstrated by specific test examples below.
Test example 1 ablation Performance test of mesophase pitch-modified phenolic resin ablation-resistant Material
1. Test method
The phenolic resin ablation resistant materials prepared in examples 1 to 3 and comparative example 1 were used for ablation performance detection according to the following test method:
ablation performance test criteria: GJB 323A-1996; heat flux density: 4100kW/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Ablation time: 30s.
2. Test results
The linear ablation rate is clearly the most important indicator for materials that have stringent requirements for maintaining aerodynamic profiles. The invention detects the linear ablation rate of each group of phenolic resin ablation resistant materials, and the result is shown in figure 1. As can be seen from fig. 1: when the flame is ablated for 5-10 s by oxyacetylene flame, the ablation expansion phenomenon occurs to both BPR and MPBPR, and the ablation expansion phenomenon is slightly improved compared with a pure one due to the introduction of MP. The ablation behavior of the material after 10-30 s of ablation is changed from ablation expansion to ablation backing, the ablation backing 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 dimension (shape maintenance) 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 macroscopic topography of the ablated surfaces of each set of phenolic resin ablation resistant materials for 5s, 10s, 20s, 30s. Obvious cracks appear on the surface of the BPR after 10 seconds of ablation, and the larger size of gaps among carbon blocks enables oxygen under the high-heat-flow oxygen-enriched condition to easily penetrate through the ablated surface of the material, so that the inside of the material is ablated and corroded. And MP was added in an amount of 5 parts (MPBPR) 5 ) 10 parts (MPBPR) 10 ) When the ablation surface needs to be flushed with oxyacetylene flame for 20s and 30s, obvious cracks appear. After adding 20 parts of MP (MPBPR) 20 ) After 30s ablation, no significant voids were observed at the ablated surface. The MP is introduced to enable the carbon layer on the surface of the material to be more compact after ablation, and oxygen is isolated outside the ablated surface of the material to a great extent, so that the ablation resistance of the material is improved.
FIG. 3 shows an MPBPR of a phenolic resin ablation resistant material 20 Composition structure study of different areas of the carbon layer after ablation. Fig. 3a is a macroscopic photograph of the surface after 5s ablation with the addition of 20 parts of mesophase pitch, and fig. 3b and 3c are XRD and infrared characterizations of different regions of the carbon layer. MPBPR 20 The colour of the ablated surface was very different from that of the edges and by observing the ablated surface topography shown in figure 2, it was found that the black edge portion of the ablated surface of the composite increased with increasing MP addition and decreasing ablation time. XRD and infrared spectra showed that the charring degree of the ablation center part is higher than that of the edge part. B is not substantially observed on XRD patterns of the central carbon layer 2 O 3 While the edge carbon layer observed significant B 2 O 3 Peak, showing that the temperature of the black edge part is lower than that of the center, B 2 O 3 Not yet volatilized. Taken together, the addition of MP effectively inhibits the diffusion of heat from the oxyacetylene ablation center to the surroundings.
Fig. 4 is an SEM photograph of a cross-section of the carbon layer after ablation of each set of phenolic resin ablation resistant materials. The carbon layer surface is smooth and compact after the ablation material is ablated, and the defects are fewer. Thus, the oxygen gas is effectively suppressed from corroding the inner resin matrix through the pyrolysis passage. In addition, due to the liquid phase carbonization process of the asphalt in the ablation process and the surface tension of the asphalt in the process, spherical structures are uniformly distributed in the carbon layer, so that 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 asphalt content. Therefore, the MP can form a spherical nano structure on the phenolic resin amorphous carbon through in-situ liquid phase carbonization in the material ablation carbonization process, so that the gap defect in the material is effectively filled, on one hand, the invasion of oxygen in an oxygen-enriched high heat flow environment to the inside is isolated, and on the other hand, the structural strength of a carbon layer of the material is increased, and the ablation resistance of the material is obviously improved.
FIG. 5 shows an MPBPR of a phenolic resin ablation resistant material 20 SEM pictures of carbon layer cross-section after ablation at different ablation times. Spherical nano structures are distributed in the carbon layer after 5s, 10s and 20s of ablation. With the continuous progress of oxyacetylene ablation, the spherical structure is gradually increased and fills up the gaps and cracks in the carbon layer. It can be observed that the material carbon layer after 5 seconds of ablation has large-area bare void defects, and the distribution of the spherical nano-structures is discontinuous. After 10s of ablation, the spherical nano-structure in the carbon layer is distributed continuously, and has certain repairing and reinforcing effects on the phenolic resin carbon layer. After the ablation is carried out for 20 seconds, the surface of the carbon layer is completely covered by the spherical nano structure, and gaps generated by pyrolysis and shrinkage cracks generated by the carbon forming process in the phenolic resin carbon 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 invention 20 SEM pictures of intermediate states of spherical structure formation in the carbon layer during ablation. As shown in the figure, an intermediate state in the formation of such a spherical structure, which is fixed due to the stopping of the oxyacetylene flame, can be clearly observed. The intermediate spherical nano structure is formed on the edge wallLamellar banding structures, which are consistent with the structure of mesophase pitch liquid crystal ordered carbons. This demonstrates that the spherical nanostructures formed during ablation are due to the liquid phase carbonization of the pitch during ablation.
Figure 7 is the XRD and raman characterization results of the central carbon layer after 4WM ablation of BPR and MPBPR composites. To verify whether the introduction of MP promotes graphitization of the carbon layer, XRD and Raman spectroscopy methods were used to collect the carbon in the ablation center in direct contact with the oxyacetylene flame. As shown in fig. 7, the XRD patterns of both pure BPR and MPBPR composites have two peaks corresponding to (002) and (101). The peak appearing around 26.0 ° is a (002) peak, corresponding to a near-graphite structure, and the peak width becomes narrower as the intensity of the peak increases (0 wt.%, 5wt.%, 10wt.%, 20 wt.%) with an increase in MP content. With the addition of MP, d002 gradually decreased and Lc gradually increased, indicating that the sample had a higher graphitization degree. Results of raman spectroscopic analysis on all samples showed that at 1360 and 1580cm -1 Two 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 the samples of MPBPR composites, indicating that graphitization of the composites was promoted. In conclusion, the mesophase pitch can form a carbonization structure with higher graphitization degree in the liquid carbonization process, which is beneficial to improving the oxidation resistance and the structural toughness of the phenolic resin ablation-resistant material.
FIG. 8 is an air atmosphere thermogravimetric analysis of a center carbon layer after 4WM ablation of a BPR and MPBPR composite. As shown in fig. 8, the thermal weight of the carbon layer after the ablation of the mesophase pitch-modified phenolic resin composite material shows that the mesophase pitch-modified carbon layer has better oxidation resistance under the 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 corroded by external oxygen-enriched heat flow, and obviously improves the anti-scouring performance of the resin matrix under the oxygen-enriched condition of high heat flow.
In summary, the invention prepares the mesophase pitch modified ablation-resistant resin matrix material, combines the liquid carbonization process of the mesophase pitch with the solid carbonization process of the resin three-dimensional crosslinked network in the ablation process, introduces the mesophase pitch liquid crystal ordered carbon structure into the carbon layer, reduces the generation of shrinkage cracks in the carbon layer, increases the graphitization degree of the mesophase pitch liquid crystal ordered carbon structure, obviously improves the anti-scouring performance of the material under the high-heat-flow oxygen-enriched condition, ensures that the formed carbon layer is more complete and compact, and further obviously improves the ablation-resistant performance of the material. The ablation-resistant resin matrix material is suitable for preparing resin-based ablation heat-resistant composite materials, and can be applied to preparing heat-resistant structures of related equipment such as high-speed aircrafts, engines and the like so as to protect structures and components which need to withstand severe environments such as high-temperature gas or pneumatic heat flow flushing.
Claims (11)
1. A mesophase pitch modified ablation-resistant resin matrix material is characterized in that: the composite material is prepared from the following raw materials in parts by weight: 120 parts of ablation-resistant resin and 30 parts of mesophase pitch; the ablation-resistant resin is phenolic resin; the intermediate phase asphalt is naphthalene intermediate phase asphalt;
the ablation-resistant resin matrix material is prepared by mixing ablation-resistant resin and mesophase pitch powder, and then performing hot pressing, curing and molding; the hot press curing molding process comprises the steps of preserving heat for 30-120 min at 100-120 ℃, preserving heat for 30-120 min after the temperature is raised from 100-120 ℃ to 140-150 ℃, preserving heat for 1-2 h after the temperature is raised from 140-150 ℃ to 180 ℃, and preserving heat for 1-2 h after the temperature is raised from 180 ℃ to 200 ℃;
the phenolic resin is boron phenolic resin.
2. The ablation-resistant resin base material according to claim 1, wherein: the hot press solidification molding process comprises the following steps: maintaining the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃ and then maintaining the temperature for 30min, heating from 140 ℃ to 180 ℃ and then maintaining the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and then maintaining the temperature for 1h;
and/or, at 110 ℃ is normal pressure; and/or the pressure is 12-15 MPa when the temperature is raised to 140-200 ℃.
3. The ablation-resistant resin base material according to claim 2, characterized in that: the temperature rising rate is 5-20 ℃ per minute.
4. The method for producing an ablation-resistant resin base material according to claim 1, characterized in that: it comprises the following steps:
(1) Crushing the ablation-resistant resin and the mesophase pitch, weighing the ablation-resistant resin and the mesophase pitch according to the weight ratio, and mixing the ablation-resistant resin and the mesophase pitch to obtain mixed powder;
(2) Hot-pressing, solidifying and molding the mixed powder, and cooling to obtain the product;
the hot press curing molding process is characterized in that the temperature is kept at 100-120 ℃ for 30-120 min, the temperature is kept at 140-150 ℃ from 100-120 ℃ for 30-120 min, the temperature is kept at 180 ℃ from 140-150 ℃ for 1-2 h, and the temperature is kept at 200 ℃ from 180 ℃ for 1-2 h.
5. The method of manufacturing according to claim 4, wherein: the hot press solidification molding process comprises the following steps: maintaining the temperature at 110 ℃ for 30min, heating from 110 ℃ to 140 ℃ and then maintaining the temperature for 30min, heating from 140 ℃ to 180 ℃ and then maintaining the temperature for 2h, and finally heating from 180 ℃ to 200 ℃ and then maintaining the temperature for 1h;
and/or, at 110 ℃ is normal pressure; and/or the pressure is 12-15 MPa when the temperature is raised to 140-200 ℃.
6. The method of manufacturing according to claim 5, wherein: the temperature rising rate is 5-20 ℃ per minute.
7. Use of the ablation-resistant resin matrix material according to any one of claims 1 to 3 for preparing materials and articles having the ablation resistance requirement.
8. Use according to claim 7, characterized in that: the material with the ablation resistance requirement and the workpiece are ablation heat-resistant composite materials.
9. Use according to claim 8, characterized in that: the ablation heat-resistant composite material is a material which is applied to the protection and sealing of structures and components in aircraft and related equipment devices, which are required to be subjected to high-temperature fuel gas and pneumatic heat flow scouring severe environments.
10. A composite material characterized by: the composite material is made of a reinforcing material and the ablation-resistant resin matrix material according to any one of claims 1-3.
11. The composite material of claim 10, wherein: the reinforcing material is a fiber and the composite material is a fiber-reinforced ablation-resistant composite material.
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