Phenolic aldehyde and hafnium ceramic precursor composite material and preparation method thereof

Abstract

The invention discloses a phenolic aldehyde and hafnium ceramic precursor composite material and a preparation method thereof. The composite material is prepared from high-carbon-content resin and filler according to the mass ratio of (15-40): (60-85). The hafnium oxide polymer is used as a filler and is mixed with the high-carbon-content resin to prepare the composite material, and the composite material has good high temperature resistance, ablation resistance and oxidation resistance and can be used as an ultrahigh-temperature thermal insulation material.

Description

Technical Field

[0001] This invention belongs to the field of composite material preparation technology, specifically relating to a phenolic and hafnium ceramic precursor composite material and its preparation method. Background Technology

[0002] With the advancement of technology, the requirements for the flight speed, reliability, and reusability of aircraft are becoming increasingly stringent, which also places higher demands on the performance of materials. For example, when aerospace vehicles enter the atmosphere, their speed can reach Mach 30, and the temperature rises sharply. Parts such as the nose cone and leading edge of the wing of the aircraft must withstand the harsh thermal environment of instantaneous ultra-high temperature and high heat flow. Therefore, it is urgent to develop a composite material that is resistant to ultra-high temperature and heat corrosion. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a phenolic resin and hafnium ceramic precursor composite material, which solves the problem of poor high temperature resistance and heat corrosion resistance of existing composite materials.

[0004] The present invention also aims to provide a method for preparing a composite material of phenolic resin and hafnium ceramic precursor.

[0005] To achieve the above objectives, the first technical solution of the present invention is as follows: a phenolic resin and hafnium ceramic precursor composite material, wherein the composite material is prepared by high carbon resin and filler in a mass ratio of (15-40):(60-85).

[0006] Furthermore, the filler is a hafnium oxide polymer.

[0007] Furthermore, the high-carbon-content resin is at least one of phenolic resin, allyl phenolic resin, epoxy-modified phenolic resin, organosilicon-modified phenolic resin, boron-modified phenolic resin, and xylene-modified phenolic resin.

[0008] The second technical solution of the present invention is implemented as follows: a method for preparing a phenolic resin and hafnium ceramic precursor composite material, comprising:

[0009] Step S1: Prepare the filler by mixing the filler with the high carbon content resin to obtain a precursor material;

[0010] Step S2: The precursor material is pyrolyzed at high temperature under vacuum or argon protection to obtain the composite material.

[0011] Further, the preparation of the precursor material in step S1 specifically involves:

[0012] HfCl4 is dissolved in an alcohol solution and reacted to generate Hf metal alkoxide, which is then chelated with a chelating agent to obtain a hafnium oxide polymer.

[0013] The high-carbon resin and hafnium oxide polymer are mixed uniformly at a mass ratio of (15-40):(60-85) to obtain a precursor material.

[0014] Further, the alcohol solution is at least one selected from ethylene glycol, propylene glycol, butanediol, n-propanol, isopropanol, and n-butanol.

[0015] Furthermore, the chelating agent is at least one of acetylacetone and ethyl acetoacetate.

[0016] Furthermore, the uniform mixing specifically involves stirring the hafnium oxide polymer and the high carbon content resin at a speed of 300 r / min to 1200 r / min for 3 h to 5 h.

[0017] Furthermore, the high-temperature pyrolysis in step S2 specifically involves raising the temperature to 1650℃~1850℃ at a rate of 30℃ / min~80℃ / min and pyrolyzing for 2h~5h.

[0018] Furthermore, in step S2, the precursor material is further cured before high-temperature pyrolysis, specifically by placing the precursor material in an oven and keeping it at 100℃, 150℃, 200℃, and 250℃ for 1h to 2h in sequence.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention uses hafnium oxide polymer as a filler and mixes it with high carbon content resin to obtain a composite material. The composite material has good high temperature resistance, ablation resistance and oxidation resistance, and can be used as an ultra-high temperature insulation material. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0021] In the description of this invention, it should be clarified that the terms "vertical," "lateral," "longitudinal," "front," "rear," "left," "right," "up," "down," and "horizontal," etc., indicating orientation or positional relationships, are based on the indicated orientation or positional relationships and are merely for the convenience of describing this invention, and do not mean that the device or element referred to must have a specific orientation or position, and therefore should not be construed as a limitation of this invention. In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installed," "connected," and "joined" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0022] The phenolic and hafnium ceramic precursor composite material provided by the present invention is prepared by high carbon content resin and filler in a mass ratio of (15-40):(60-85), wherein the filler is a hafnium oxide polymer.

[0023] The high-carbon-content resin is at least one of phenolic resin, allyl phenolic resin, epoxy-modified phenolic resin, organosilicon-modified phenolic resin, boron-modified phenolic resin, and xylene-modified phenolic resin.

[0024] The preparation method of the above-mentioned phenolic resin and hafnium ceramic precursor composite material includes:

[0025] Step S1: HfCl4 is dissolved in an alcohol solution to react and generate Hf metal alkoxide. Then, a chelating agent is added for chelation to obtain hafnium oxide polymer. The high carbon content resin and the filler are mixed at a mass ratio of (15-40):(60-85) and stirred at 300r / min-1200r / min for 3-5 hours to obtain precursor material.

[0026] The alcohol solution is at least one of ethylene glycol, propylene glycol, butanediol, n-propanol, isopropanol, and n-butanol, and the chelating agent is at least one of acetylacetone and ethyl acetoacetate.

[0027] Step S2: Place the precursor material in an oven and heat it sequentially at 100℃, 150℃, 200℃, and 250℃ for 1h to 2h. Then, under vacuum or argon protection, raise the temperature of the precursor material to 1650℃ to 1850℃ at a rate of 30℃ / min to 80℃ / min and pyrolyze it for 2h to 5h to obtain the composite material.

[0028] Example 1

[0029] The phenolic and hafnium ceramic precursor composite material provided in this embodiment is prepared by high carbon resin and filler in a mass ratio of 15:85.

[0030] The high-carbon resin is a phenolic resin, and the filler is a hafnium oxide polymer.

[0031] This invention uses hafnium oxide polymer as a filler and mixes it with high carbon content resin to obtain a composite material. This composite material has good high temperature resistance, ablation resistance and oxidation resistance, and can be used as an ultra-high temperature insulation material.

[0032] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.2 mg / s to 1.45 mg / s, and the linear ablation rate was 0.0025 mm / s to 0.0039 mm / s.

[0033] Example 2

[0034] The phenolic and hafnium ceramic precursor composite material provided in this embodiment is prepared by high carbon resin and filler in a mass ratio of 25:75.

[0035] The high-carbon resin is an allylphenolic resin, and the filler is a hafnium oxide polymer.

[0036] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.03 mg / s to 1.38 mg / s, and the linear ablation rate was less than 0.00235 mm / s to 0.00359 mm / s.

[0037] Example 3

[0038] The phenolic and hafnium ceramic precursor composite material provided in this embodiment is prepared by high carbon resin and filler in a mass ratio of 30:70.

[0039] The high-carbon resin is an organosilicon-modified phenolic resin, and the filler is a hafnium oxide polymer.

[0040] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.06 mg / s to 1.105 mg / s, and the linear ablation rate was less than 0.00243 mm / s to 0.00358 mm / s.

[0041] Example 4

[0042] The phenolic and hafnium ceramic precursor composite material provided in this embodiment is prepared by high carbon resin and filler in a mass ratio of 40:60.

[0043] The high-carbon resin is boron-modified phenolic resin, and the filler is hafnium oxide polymer.

[0044] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.26 mg / s to 1.44 mg / s, and the linear ablation rate was less than 0.00252 mm / s to 0.00349 mm / s.

[0045] Example 5

[0046] The preparation process of the phenolic resin and hafnium ceramic precursor composite material as described in Example 3 is as follows:

[0047] Step S1: Mix the filler with the high carbon content resin to obtain a precursor material.

[0048] Specifically, HfCl4 is dissolved in an alcohol solution to react and generate Hf metal alkoxide, which is then chelated with a chelating agent to obtain a hafnium oxide polymer. The hafnium oxide polymer is then stirred with a high-carbon resin at 300 r / min for 5 h to obtain a precursor material.

[0049] The alcohol solution is ethylene glycol, propylene glycol, butanediol, n-propanol, isopropanol, or n-butanol, and the chelating agent is acetylacetone or ethyl acetoacetate.

[0050] Step S2: Place the precursor material in an oven and keep it at 100℃, 150℃, 200℃, and 250℃ for 1 hour at each temperature. Then, under vacuum or argon protection, raise the temperature of the precursor material to 1650℃ at a rate of 30℃ / min and pyrolyze it for 5 hours to obtain the composite material.

[0051] The above preparation process first synthesizes hafnium oxide polymer using a precursor method, then mixes it with a high-carbon resin to obtain a precursor material. The composite material is obtained by curing and high-temperature pyrolysis of the precursor material. The reaction conditions in this process are mild and the requirements for equipment are low. The resulting composite material has excellent high-temperature resistance, ablation resistance and oxidation resistance.

[0052] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.06 mg / s, and the linear ablation rate was less than 0.00246 mm / s.

[0053] Example 6

[0054] The preparation process of the phenolic resin and hafnium ceramic precursor composite material as described in Example 3 is as follows:

[0055] Step S1: Mix the filler with the high-carbon resin to obtain a precursor material;

[0056] Specifically, a hafnium oxide polymer is prepared by stirring the hafnium oxide polymer with a high carbon content resin at 800 r / min for 4 h to obtain a precursor material.

[0057] Step S2: Place the precursor material in an oven and keep it at 100℃, 150℃, 200℃, and 250℃ for 1.5 hours in sequence. Then, under vacuum or argon protection, raise the temperature of the precursor material to 1750℃ at a rate of 50℃ / min and decompose it for 3 hours to obtain the composite material.

[0058] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.105 mg / s, and the linear ablation rate was less than 0.00253 mm / s.

[0059] Example 7

[0060] The preparation process of the phenolic resin and hafnium ceramic precursor composite material as described in Example 3 is as follows:

[0061] Step S1: Mix the filler with the high-carbon resin to obtain a precursor material;

[0062] Specifically, a hafnium oxide polymer is prepared by stirring the hafnium oxide polymer with a high carbon content resin at 1200 r / min for 3 hours to obtain a precursor material.

[0063] Step S2: Place the precursor material in an oven and keep it at 100℃, 150℃, 200℃, and 250℃ for 2 hours in sequence. Then, under vacuum or argon protection, raise the temperature of the precursor material to 1850℃ at a rate of 80℃ / min and decompose it for 2 hours to obtain the composite material.

[0064] Using the ablation test equipment described in national standard GJB323A-96, the composite material described in this embodiment was subjected to an oxyacetylene ablation test. The mass ablation rate was 1.079 mg / s, and the linear ablation rate was less than 0.00243 mm / s.

[0065] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A phenolic resin and hafnium ceramic precursor composite material, characterized in that, The composite material is prepared by high carbon content resin and filler in a mass ratio of (15-40):(60-85).

2. The phenolic resin and hafnium ceramic precursor composite material according to claim 1, characterized in that, The filler is a hafnium oxide polymer.

3. The phenolic and hafnium ceramic precursor composite material according to claim 1, characterized in that, The high-carbon-content resin is at least one of phenolic resin, allyl phenolic resin, epoxy-modified phenolic resin, organosilicon-modified phenolic resin, boron-modified phenolic resin, and xylene-modified phenolic resin.

4. A method for preparing a phenolic resin and hafnium ceramic precursor composite material according to any one of claims 1-3, characterized in that, include: Step S1: Prepare the filler by mixing the filler with the high carbon content resin to obtain a precursor material; Step S2: The precursor material is pyrolyzed at high temperature under vacuum or argon protection to obtain the composite material.

5. The method for preparing a phenolic resin and hafnium ceramic precursor composite material according to claim 4, characterized in that, The preparation of the precursor material in step S1 specifically involves: HfCl4 is dissolved in an alcohol solution and reacted to generate Hf metal alkoxide, which is then chelated with a chelating agent to obtain a hafnium oxide polymer. The high-carbon resin and hafnium oxide polymer are mixed uniformly at a mass ratio of (15-40):(60-85) to obtain a precursor material.

6. The method for preparing a phenolic and hafnium ceramic precursor composite material according to claim 5, characterized in that, The alcohol solution is at least one of ethylene glycol, propylene glycol, butanediol, n-propanol, isopropanol, and n-butanol.

7. The method for preparing a phenolic and hafnium ceramic precursor composite material according to claim 6, characterized in that, The chelating agent is at least one of acetylacetone and ethyl acetoacetate.

8. The method for preparing a phenolic and hafnium ceramic precursor composite material according to claim 5, characterized in that, The process of achieving uniform mixing specifically involves stirring the hafnium oxide polymer and the high-carbon resin at a speed of 300 r / min to 1200 r / min for 3 to 5 hours.

9. The method for preparing a phenolic resin and hafnium ceramic precursor composite material according to claim 4, characterized in that, The high-temperature pyrolysis in step S2 specifically involves raising the temperature to 1650℃~1850℃ at a rate of 30℃ / min~80℃ / min and pyrolyzing for 2h~5h.

10. The method for preparing a phenolic and hafnium ceramic precursor composite material according to claim 4, characterized in that, Before high-temperature pyrolysis in step S2, the precursor material is further cured, specifically by placing the precursor material in an oven and keeping it at 100℃, 150℃, 200℃, and 250℃ for 1 to 2 hours in sequence.