Search

CN-121991459-A - Antioxidant and anti-scouring heat-proof composite material, preparation method and application

CN121991459ACN 121991459 ACN121991459 ACN 121991459ACN-121991459-A

Abstract

The invention discloses an anti-oxidation anti-scouring heat-proof composite material, a preparation method and application thereof, and belongs to the technical field of high-temperature heat-proof materials. The method comprises the steps of reacting hydrolyzed organosilane with phenolic resin to obtain silicon modified phenolic resin, bonding with an organoboron compound to obtain boron-silicon co-modified phenolic resin, adding a curing agent, injecting into a fiber reinforcement mould, performing sol-gel reaction and drying at normal pressure to obtain the finished product. The invention makes boron and silicon element embed into phenolic molecular chain by covalent bond to form boron-silicon-carbon hybridization network, and generates nano ceramic phase and compact glassy protection layer at high temperature, and has excellent scouring resistance, thermal stability and heat insulation. The preparation process is simple and controllable, is suitable for large-scale production, can accurately regulate and control the performance of the material, and is suitable for heat protection components of supersonic aircrafts.

Inventors

  • Request for anonymity
  • Request for anonymity
  • Request for anonymity

Assignees

  • 蚌埠凌空科技有限公司

Dates

Publication Date
20260508
Application Date
20260318

Claims (10)

  1. 1. The preparation method of the antioxidant and anti-scouring heat-proof composite material is characterized by comprising the following steps of: S1, reacting hydrolyzed organosilane with phenolic resin to obtain silicon modified phenolic resin; S2, reacting the silicon modified phenolic resin with an organic boron compound to obtain boron-silicon co-modified phenolic resin; s3, adding a curing agent into the boron-silicon co-modified phenolic resin, injecting the curing agent into a die provided with a fiber reinforcement in advance, and performing sol-gel reaction to obtain a wet gel composite; S4, drying the wet gel composite body to obtain the anti-oxidation anti-scouring heat-proof composite material.
  2. 2. The preparation method according to claim 1, wherein the preparation method of the hydrolyzed organosilane in the step S1 comprises the following steps: Adding the organosilane into an ethanol water solution, adjusting the pH of the solution to 4-5, and stirring for 20-40 min at 20-30 ℃ to obtain hydrolyzed organosilane; preferably, the addition amount of the organosilane is 20-40 wt% of the mass of the ethanol water solution; preferably, the volume ratio of water to ethanol in the aqueous solution of ethanol is (1:9) - (1:4).
  3. 3. The method according to claim 1, wherein the phenolic resin in step S1 is a novolac phenolic resin having a number average molecular weight Mn of 800 to 1200, a free phenol content of less than 0.1%, and a softening point of 110 to 135 ℃.
  4. 4. The method according to claim 3, wherein the organosilane in step S1 comprises at least one of vinyltriethoxysilane, vinyltrimethoxysilane, and phenyltriethoxysilane.
  5. 5. The preparation method according to claim 4, wherein the mass ratio of the organosilane to the phenolic resin is (1:10) - (3:10).
  6. 6. The method of claim 1, wherein the organoboron compound of step S2 comprises at least one of triethylborate, trimethylborate, triisopropylborate, or phenylboronic acid; preferably, the addition amount of the organoboron compound is 4wt.% to 10wt.% of the mass of the phenolic resin in the step S1; Preferably, the reaction temperature of the silicon modified phenolic resin and the organoboron compound in the step S2 is 50-80 ℃ and the reaction time is 2-6 hours.
  7. 7. The preparation method according to claim 1, wherein the addition amount of the curing agent in the step S3 is 10wt.% to 14wt.% of the mass of the phenolic resin in the step S1.
  8. 8. The method according to claim 7, wherein the sol-gel reaction temperature is 90-110 ℃ and the reaction time is 12-36 hours.
  9. 9. An oxidation-resistant, scour-resistant, heat-resistant composite material made according to the method of any one of claims 1-8.
  10. 10. Use of an oxidation-resistant erosion-resistant insulation composite according to claim 9 in a thermal protection component of a supersonic aircraft.

Description

Antioxidant and anti-scouring heat-proof composite material, preparation method and application Technical Field The invention relates to the technical field of high-temperature heat protection materials, in particular to an anti-oxidation anti-scouring heat-proof composite material, a preparation method and application. Background When the supersonic aircraft passes through the atmosphere, air molecules are accumulated and compressed in front of the supersonic aircraft to form shock waves, so that intense pneumatic heating is induced, the surface temperature of the supersonic aircraft rises along with Mach number, the temperature reaches 1200 ℃ at Mach 6 and exceeds 2000 ℃ above Mach 10, and the heat load of key parts such as the head, the front edge of the wing and the like is particularly outstanding. Along with the development of aerospace technology, the thermal protection material needs to have the characteristics of light weight, ultrahigh temperature resistance and oxidation resistance, also needs to bear extreme heat flow, temperature gradient and thermal stress, adapts to complex structure integration and reliably blocks heat, and protects internal equipment and components. The phenolic resin is a classical ablation protective matrix material, has high carbon residue rate and excellent thermal stability, can dissipate energy through a physical and chemical process of high-temperature ablation, and a protective layer formed by an ablation product can also block heat and alleviate pneumatic heating corrosion. However, the phenolic aerogel has insufficient skeleton strength after carbonization, poor high-temperature airflow scouring resistance and easy structural collapse to cause rapid heat transfer, and the existing modification mode of physically blending inorganic filler is easy to cause the problems of uneven sedimentation and dispersion of filler, deterioration of heat insulation performance, cracking of high-temperature coating and the like, and the process of surface dipping and coating inorganic slurry is tedious and low-efficiency, thus being not beneficial to large-scale production. At present, the phenolic resin is modified by high-temperature resistant elements such as boron, silicon and the like, so that the ablation resistance of the aerogel is improved, and the modified phenolic resin is a modification mode with simple and convenient process and strong practicability. The conventional boron-silicon co-modified phenolic aerogel is mainly prepared by physically mixing boric acid and a common silane coupling agent, wherein the boron-silicon and a phenolic matrix are only in weak interaction, the interface combination property is poor, the brittleness of the framework is large, the framework is easy to crack and pulverize when facing high-speed heat flow flushing, and the severe anti-flushing environment requirement of a supersonic aircraft under high Mach number cannot be met. Disclosure of Invention In order to overcome the defects in the prior art, the invention realizes silicon modification by firstly hydrolyzing organosilane and dehydrating and copolymerizing phenolic resin, and then introduces boron compound and silicon modified phenolic resin to generate bonding reaction, so that boron silicon element is embedded into phenolic molecular chain in a covalent bond form, thereby not only retaining the high temperature resistance of phenolic aerogel, but also obviously improving the toughness and interface bonding strength of the skeleton and solving the technical bottleneck of insufficient anti-scouring performance. The invention aims at providing a preparation method of an antioxidant and anti-scouring heat-proof composite material, which comprises the following steps: S1, reacting hydrolyzed organosilane with phenolic resin to obtain silicon modified phenolic resin; S2, reacting the silicon modified phenolic resin with an organic boron compound to obtain boron-silicon co-modified phenolic resin; s3, adding a curing agent into the boron-silicon co-modified phenolic resin, injecting the curing agent into a die provided with a fiber reinforcement in advance, and performing sol-gel reaction to obtain a wet gel composite; S4, drying the wet gel composite body to obtain the anti-oxidation anti-scouring heat-proof composite material. Preferably, the preparation method of the hydrolyzed organosilane in the step S1 comprises the following steps: Adding the organosilane into an ethanol water solution, adjusting the pH of the solution to 4-5, and stirring for 20-40 min at 20-30 ℃ to obtain hydrolyzed organosilane; preferably, the addition amount of the organosilane is 20-40 wt% of the mass of the ethanol water solution; preferably, the volume ratio of water to ethanol in the aqueous solution of ethanol is (1:9) - (1:4). Preferably, the phenolic resin in the step S1 is a linear phenolic resin, the number average molecular weight Mn of the phenolic resin is 800-1200, the free phenol content is les