CN115850906A - Modified high-temperature ablation-resistant heat-insulation composite material and preparation method thereof - Google Patents
Modified high-temperature ablation-resistant heat-insulation composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002679 ablation Methods 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000009413 insulation Methods 0.000 title claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 105
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 40
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- 239000000243 solution Substances 0.000 claims abstract description 35
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- 238000010438 heat treatment Methods 0.000 claims abstract description 26
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
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- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention provides a modified high-temperature ablation-resistant heat-insulating composite material and a preparation method thereof, belonging to the technical field of heat protection materials, wherein the preparation method comprises the following steps: mixing a titanium dioxide precursor, a silicon dioxide precursor, a silane coupling agent, a first solvent and an acidic solution to obtain a first impregnation solution, placing the fiber woven body in the first impregnation solution, and performing first impregnation, gelation treatment, aging treatment and heat treatment to obtain a modified woven body; mixing phenolic resin, nano titanium dioxide and a second solvent to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, and performing second impregnation and first precuring to obtain a pretreated modified braided body; and (3) carrying out third impregnation, fourth impregnation, second precuring, curing, solvent replacement and normal-pressure drying on the pretreated modified woven body to obtain the modified high-temperature ablation-resistant heat-insulation composite material. The preparation process is simple, and the prepared modified high-temperature ablation-resistant heat-insulating composite material has excellent ablation resistance and oxidation resistance.
Description
Technical Field
The invention belongs to the technical field of thermal protection materials, and particularly relates to a modified high-temperature ablation-resistant heat-insulation composite material and a preparation method thereof.
Background
Along with the improvement of service requirements, extremely harsh requirements are provided for the temperature resistance, durability, structural efficiency and reliability of the thermal protection material, so that researchers are prompted to change the traditional material design concept and continuously research and develop novel thermal protection materials.
TiO 2 As a ceramic material, it is widely added to various aerogel materials due to its excellent oxidation resistance; however, conventional physical doping does not achieve added TiO 2 Uniform distribution of particles; at the same time, due to TiO 2 The defect of weak self-framework strength, so that the existing TiO 2 Most of aerogel materials need to adopt freeze drying and supercritical drying processes, and the batch production of the materials cannot be realizedProduction, and limits the application field.
Therefore, there is an urgent need to develop a method for converting TiO into TiO 2 The preparation method can be used for realizing batch production by uniformly introducing the aerogel material.
Disclosure of Invention
The preparation method provided by the invention has the advantages of simple process and short period, and can be used for mass production, and the prepared modified high-temperature ablation-resistant heat-insulating composite material has excellent ablation resistance and oxidation resistance.
The invention provides a preparation method of a modified high-temperature ablation-resistant heat-insulation composite material in a first aspect, which comprises the following steps:
s1, mixing a titanium dioxide precursor, a silicon dioxide precursor, a silane coupling agent, a first solvent and an acidic solution to obtain a first impregnation liquid, placing a fiber woven body into the first impregnation liquid, and performing first impregnation, gelation treatment, aging treatment and heat treatment to obtain a modified woven body;
s2, mixing phenolic resin, nano titanium dioxide and a second solvent to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, and performing second impregnation and first precuring to obtain a pretreated modified braided body;
s3, carrying out third impregnation, fourth impregnation, second precuring, curing, solvent replacement and normal-pressure drying on the pretreated modified braided body to obtain a modified high-temperature ablation-resistant heat-insulation composite material; the third impregnation liquid for carrying out the third impregnation is obtained by mixing phenolic resin, a curing agent, nano titanium dioxide and a third solvent; and the fourth impregnation liquid for performing the fourth impregnation is obtained by mixing phenolic resin, a curing agent and a third solvent.
Preferably, in step S1, the molar ratio of the titanium dioxide precursor, the silicon dioxide precursor, the silane coupling agent, the first solvent and the solute in the acidic solution is 1 (0-1): 0-1: (21-42): 1-4, wherein the molar numbers of the silicon dioxide precursor and the silane coupling agent are not 0 at the same time;
preferably, in step S1, the titanium dioxide precursor is selected from one or more of butyl titanate, titanium isopropoxide and titanium butoxide;
the silicon dioxide precursor is tetraethoxysilane;
the silane coupling agent is selected from one or more of methyltrimethoxysilane, dimethyldiethoxysilane, gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane;
the first solvent is ethanol solution; preferably, the molar ratio of the ethanol to the water in the first solvent is (18-36) to (3-6); and/or
The acid solution is one or more of glacial acetic acid, hydrochloric acid and nitric acid.
Preferably, in step S1, the fiber braid is made of carbon fiber, quartz fiber, glass fiber or mullite fiber; preferably, the fiber woven body is a continuous fiber needle punched structure, a net tire structure, a 2.5D woven structure or a three-dimensional woven structure; more preferably, the fiber woven body has a length of 30. + -.10 cm, a width of 30. + -.10 cm and a thickness of 10. + -.5 cm.
Preferably, in step S1, the temperature of the gelation treatment is 80 to 100 ℃;
the temperature of the aging treatment is 100-120 ℃, and the time is 3-6 h; and/or
The heat treatment is to heat up to 400-600 ℃ at the heating rate of 4-10 ℃/min and keep the temperature for 1.5-3.5 h.
Preferably, in the step S2, the mass ratio of the phenolic resin, the nano titanium dioxide and the second solvent in the second impregnation liquid is (20-40): (0.2-2): (100-120);
the first pre-curing is heat preservation for 10 to 20 hours at a temperature of between 100 and 120 ℃.
Preferably, in step S3, the mass ratio of the phenolic resin, the nano titanium dioxide, the curing agent and the third solvent in the third impregnation liquid is 20 (0.2-1): 1-5): 80-120;
the temperature of the third impregnation is 70-80 ℃, and the time is 30-60 min; preferably, the third impregnation is performed to an impregnation depth of 1 to 5cm.
Preferably, in the step S3, the mass ratio of the phenolic resin, the curing agent and the third solvent in the fourth impregnation liquid is 20 (1-5) to (80-120);
the temperature of the second precuring is 80-100 ℃;
the curing is carried out for 5 to 30 hours at the temperature of between 150 and 180 ℃; and/or
The temperature of the normal pressure drying is 170-190 ℃.
Preferably, the second solvent is one or more of absolute ethyl alcohol, acetone, toluene and n-hexane;
the third solvent is one or more of absolute ethyl alcohol, deionized water, propanol, methanol and glycol; and/or
The curing agent is one or more of paraformaldehyde, hexamethylenetetramine, aniline, formaldehyde and melamine.
The invention provides a modified high-temperature ablation-resistant heat-insulating composite material in a second aspect, which is prepared by the preparation method described above.
Compared with the prior art, the invention at least has the following beneficial effects:
the invention can form TiO on the surface and inside of the modified braid by blending the titanium dioxide precursor and the silicon dioxide precursor, and then carrying out cogelling treatment, aging treatment and heat treatment 2 And SiO 2 Homogeneously distributed TiO 2 -SiO 2 Compounding aerogel; the invention realizes TiO through the mode of blending and cogelling the titanium dioxide precursor and the silicon dioxide precursor 2 The uniform introduction of the modified high-temperature ablation-resistant heat-insulating composite material improves the ablation resistance and the oxidation resistance of the modified high-temperature ablation-resistant heat-insulating composite material, and overcomes the defect that the TiO is traditionally doped in a physical doping way 2 Introduction into aerogel materials fails to achieve TiO 2 The problem of uniform distribution of particles.
The invention leads the prepared titanium dioxide precursor and the silicon dioxide precursor to be blended and cogelledContaining TiO 2 -SiO 2 The modified high-temperature ablation-resistant heat-insulation composite material of the composite aerogel can be dried under the normal pressure condition, the preparation cost is greatly reduced, the preparation period is shortened, the composite aerogel can be used for batch production, and the problem that TiO in the prior art is caused 2 The defect of weak self-skeleton strength, so that the TiO 2 The aerogel material mostly adopts freeze drying and supercritical drying processes, the mass production of the material cannot be realized, and the application field of the modified high-temperature ablation-resistant heat-insulating composite material is widened.
The strength of the modified high-temperature ablation-resistant heat-insulating composite material is improved by introducing the fiber braid and the TiO is uniformly introduced 2 The oxidation of the fiber braided body in a high-temperature environment is reduced to a certain extent, and the structural stability of the composite material is improved.
The preparation method of the modified high-temperature ablation-resistant heat-insulating composite material is simple in process, short in preparation period and suitable for batch production, and the prepared composite material is low in density, good in heat resistance and low in ablation rate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a diagram of a modified high temperature ablation-resistant thermal insulation composite material provided in example 1 of the present invention before (left) and after (right) ablation with oxyacetylene;
FIG. 2 is a diagram of a modified high temperature ablation resistant thermal insulation composite material provided in example 3 of the present invention before (left) and after (right) ablation with oxyacetylene;
FIG. 3 is a microstructure diagram of a modified braid prepared in example 1 of the present invention;
FIG. 4 is a microstructure diagram of a pretreated modified knit fabric prepared in example 1 of the present invention;
FIG. 5 is a microstructure diagram of a modified high temperature ablation resistant thermal insulation composite prepared in example 1 of the present invention;
FIG. 6 is a TG curve of the modified high temperature ablation resistant thermal insulation composite prepared in example 1, example 2 and comparative example 1 of the present invention;
FIG. 7 is a graph showing the change of the surface temperature and the back temperature with time in the oxyacetylene ablation process of the modified high-temperature ablation-resistant heat-insulating composite material prepared in example 3 of the present invention;
FIG. 8 is a microstructure view of a composite material prepared in comparative example 2 of the present invention;
FIG. 9 is a microstructure diagram of a modified braid prepared in comparative example 3 of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the following embodiments will be clearly and completely described in conjunction with the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
The invention provides a preparation method of a modified high-temperature ablation-resistant heat-insulating composite material in a first aspect, which comprises the following steps:
s1, mixing a titanium dioxide precursor, a silicon dioxide precursor, a silane coupling agent, a first solvent and an acidic solution to obtain a first impregnation liquid, placing a fiber woven body into the first impregnation liquid, and performing first impregnation, gelation treatment, aging treatment and heat treatment to obtain a modified woven body;
s2, mixing phenolic resin, nano titanium dioxide and a second solvent to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, and performing second impregnation and first precuring to obtain a pretreated modified braided body;
s3, carrying out third impregnation, fourth impregnation, second precuring, curing, solvent replacement and normal-pressure drying on the pretreated modified braided body to obtain a modified high-temperature ablation-resistant heat-insulation composite material; the third impregnation liquid for carrying out the third impregnation is obtained by mixing phenolic resin, a curing agent, nano titanium dioxide and a third solvent; and the fourth impregnation liquid for performing the fourth impregnation is obtained by mixing phenolic resin, a curing agent and a third solvent.
In the present invention, the impregnation may be atmospheric pressure impregnation or vacuum impregnation; wherein the normal pressure impregnation pressure is 101.3kPa, and the vacuum impregnation pressure is 0.01-10 kPa; the dipping temperature is normal temperature if not specially stated; the solvent replacement of the invention uses absolute ethyl alcohol as solvent, and the solvent is replaced every 4 to 6 hours, and the replacement times of the solvent are 3 to 5 times.
According to the invention, a titanium dioxide precursor and a silicon dioxide precursor are blended and then hydrolyzed respectively to generate a Si-OH structure and a Ti-OH structure, and the Si-O-Si structure, the Ti-O-Ti structure and the Si-O-Ti structure are obtained through further condensation, so that a chain structure and a net structure containing Si and Ti are formed; in this way, si and Ti are uniformly distributed in the first impregnation liquid in the form of a compound, can be uniformly filled on the surface and the inside of the fiber woven fabric in the impregnation process, and then TiO can be formed on the surface and the inside of the modified woven fabric through gelation treatment, aging treatment and heat treatment 2 And SiO 2 Homogeneously distributed TiO 2 -SiO 2 And (3) compounding the aerogel.
The invention can form TiO on the surface and inside of the modified braid by blending the titanium dioxide precursor and the silicon dioxide precursor, and then carrying out cogelling treatment, aging treatment and heat treatment 2 And SiO 2 Homogeneously distributed TiO 2 -SiO 2 Compounding aerogel; the invention realizes TiO through the mode of blending and cogelling the titanium dioxide precursor and the silicon dioxide precursor 2 The uniform introduction of the titanium dioxide improves the ablation resistance and the oxidation resistance of the modified high-temperature ablation-resistant heat-insulation composite material, and overcomes the defect that the TiO is doped in a physical doping way in the prior art 2 Introduction into aerogel materials fails to achieve TiO 2 The problem of uniform distribution of particles.
The invention is prepared by mixing a titanium dioxide precursor and silicon dioxideThe mode of body blending and co-gelation treatment enables the prepared TiO-containing material 2 -SiO 2 The modified high-temperature ablation-resistant heat-insulation composite material of the composite aerogel can be dried under the normal pressure condition, the preparation cost is greatly reduced, the preparation period is shortened, the composite aerogel can be used for batch production, and the problem that TiO in the prior art is caused 2 The defect of weak self-skeleton strength, so that Ti O 2 The aerogel material mostly adopts freeze drying and supercritical drying processes, the mass production of the material cannot be realized, and the application field of the modified high-temperature ablation-resistant heat-insulating composite material is widened.
The strength of the modified high-temperature ablation-resistant heat-insulating composite material is improved by introducing the fiber braid and the TiO is uniformly introduced 2 The oxidation of the fiber braided body in a high-temperature environment is reduced to a certain extent, and the structural stability of the composite material is improved.
According to some preferred embodiments, in step S1, the molar ratio of the titania precursor, the silica precursor, the silane coupling agent, the first solvent, and the solute in the acidic solution is 1 (0 to 1): 0 to 1 (21 to 42): 1 to 4, wherein the molar numbers of the silica precursor and the silane coupling agent are not 0 at the same time; the silicon dioxide precursor and the silane coupling agent are mainly used as silicon sources, and the silicon dioxide precursor and the silane coupling agent are only required to be used in different amounts of 0.
In some preferred embodiments, the molar ratio of the titania precursor, the silica precursor, the silane coupling agent, the first solvent, and the solute in the acidic solution is 1 (0.1-1): 0.1-1: (21-42): 1-4).
According to some preferred embodiments, in step S1, the titanium dioxide precursor is selected from one or more of butyl titanate, titanium isopropoxide, titanium butoxide;
the silicon dioxide precursor is tetraethoxysilane;
the silane coupling agent is selected from one or more of methyltrimethoxysilane, dimethyldiethoxysilane, gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane;
the first solvent is ethanol solution; preferably, the molar ratio of the ethanol to the water in the first solvent is (18-36) to (3-6); according to the invention, the first solvent is selected from an ethanol solution, and firstly plays a role in dispersing a titanium dioxide precursor, a silicon dioxide precursor and a silane coupling agent; more importantly, water mainly provides hydrolysis conditions for hydrolysis of the titanium dioxide precursor, the silicon dioxide precursor and the silane coupling agent, and the hydrolysis speed of the titanium dioxide precursor, the silicon dioxide precursor and the silane coupling agent is too high and precipitates are easy to generate by only taking water as a solvent; the addition of the ethanol plays a role in slowing down the hydrolysis rate, so that precipitation caused by too fast hydrolysis is avoided, and the first impregnation liquid which is uniformly dispersed cannot be obtained; and/or
The acid solution is one or more of glacial acetic acid, hydrochloric acid and nitric acid; the purpose of adding the acidic solution is to inhibit hydrolysis to a certain extent, and avoid the problem that the first impregnation liquid which is uniformly dispersed cannot be obtained due to precipitation caused by overlarge hydrolysis degree of the titanium dioxide precursor, the silicon dioxide precursor and the silane coupling agent in the mixing process.
According to some preferred embodiments, in step S1, the fiber braid is made of carbon fiber, quartz fiber, glass fiber, or mullite fiber; preferably, the fiber knitted body is a continuous fiber needle punched structure, a net tire structure, a 2.5D knitted structure or a three-dimensional knitted structure; more preferably, the fiber woven body has a length of 30. + -.10 cm, a width of 30. + -.10 cm and a thickness of 10. + -.5 cm.
According to some preferred embodiments, in step S1, the temperature of the gelation treatment is 80 to 100 ℃ (for example, may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, or 100 ℃); the temperature of the aging treatment is 100 to 120 ℃ (for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃) and the time is 3 to 6 hours (for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours);
because the hydrolysis and condensation rate of the titanium dioxide precursor and the silicon dioxide precursor is slow at normal temperature, the temperature of the gelation treatment is controlled between 80 and 100 ℃, and the titanium dioxide precursor and the silicon dioxide precursor can be acceleratedThe time required for the gelation process is shortened, and TiO is finally formed on the surface and inside of the fiber woven body 2 -SiO 2 Compounding the wet gel; the invention carries out aging treatment after gelation treatment, and aims to ensure complete gelation treatment process so as to ensure that wet gel with more complete structure and more stable performance is obtained on the surface of the fiber woven fabric.
The heat treatment is carried out at a temperature rise rate of 4 to 10 ℃/min (e.g., 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min) to 400 to 600 ℃ (e.g., 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ or 600 ℃) and at a temperature rise rate of 4 to 10 ℃/min (e.g., 1.5h, 2h, 2.5h, 3h or 3.5 h).
The invention can lead TiO to be treated by the heat treatment process 2 -SiO 2 Removing solvent from the composite wet gel to form TiO on the surface and inside of the fiber woven body 2 -SiO 2 Compounding aerogel; more importantly, the heat treatment of the present invention is to convert the partially amorphous titanium dioxide to crystalline titanocerite-type titanium dioxide; in the ablation process, the anatase titanium dioxide particles can be used as crystal nuclei to promote the conversion of titanium dioxide in the composite material to rutile titanium dioxide, and the generated rutile titanium dioxide can effectively shield infrared radiation and reduce the surface temperature of the material; furthermore, the conversion process of the rutile type titanium dioxide can also absorb the heat in the ablation process of the composite material, further reduce the surface temperature of the material and improve the ablation resistance of the composite material. Furthermore, during ablation, the SiO in the composite material 2 Can form a liquid film, can isolate oxygen and heat, further improve the oxidation resistance of the composite material and reduce the surface temperature of the composite material.
According to some preferred embodiments, in the step S2, the mass ratio of the phenolic resin, the nano titanium dioxide and the second solvent in the second impregnation liquid is (20-40): (0.2-2): (100-120);
the first pre-curing is performed by heat-preserving at 100 to 120 ℃ (e.g., 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃) for 10 to 20 hours (e.g., 10 hours, 12 hours, 14 hours, 16 hours, 18 hours or 20 hours).
In the heat treatment process, the solvent (comprising the first solvent and organic matters such as titanium dioxide precursor, silicon dioxide precursor, alcohols generated by hydrolysis of silane coupling agent and the like) in the wet gel volatilizes to enable gaps to exist on the surface of the modified woven fabric (as shown in figure 3), so that the modified woven fabric is further pretreated, and the gaps on the surface of the modified woven fabric are filled with the mixture of phenolic resin, nano titanium dioxide and the second solvent, so that the structure and the performance of the obtained pretreated modified woven fabric (as shown in figure 4) are more uniform.
It is apparent from FIGS. 3 to 4 (the same magnification view) that the gaps on the surface of the pretreated modified knitted fabric after the caulking treatment are significantly reduced, and the large pieces of the fabric in FIG. 4 are significantly peeled off during the sample preparation.
According to some preferred embodiments, in the step S3, the mass ratio of the phenolic resin, the nano titanium dioxide, the curing agent and the third solvent in the third impregnation liquid is 20 (0.2-1): 1-5): 80-120;
in some specific embodiments, the phenolic resin, the curing agent and the third solvent are uniformly mixed, and then the nano titanium dioxide powder is added under the stirring condition to prepare a third impregnation liquid in which the nano titanium dioxide powder is uniformly dispersed; in order to accelerate the mixing process, the mixing temperature can be properly raised, for example, the nano titanium dioxide powder can be added at the temperature of 50-60 ℃.
The third impregnation is carried out at a temperature of 70 to 80 ℃ (for example, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃) for 30 to 60min (for example, 30min, 35min, 40min, 45min, 50min, 55min or 60 min); preferably, the third impregnation is performed to an impregnation depth of 1 to 5cm.
The third impregnation is to perform partial impregnation on the pretreated modified braided body, the impregnation is performed along the thickness direction of the pretreated modified braided body, the impregnation depth is 1-5 cm, and the third impregnation is used for performing strengthening treatment on the part, close to a heat source, of the surface of the pretreated modified braided body so as to improve the oxidation resistance and the ablation resistance of the pretreated modified braided body; the temperature of the third impregnation is controlled to be 70-80 ℃, so that the viscosity of the third impregnation liquid can be increased to a certain extent, the nano titanium dioxide powder is prevented from sinking, the effect of fixing the nano titanium dioxide powder is achieved, and the uniformity of the impregnation is ensured; in the actual use process, the ablation effect on the surface layer of the composite material is obvious, and the dipping depth can be selected according to the actual requirement; the dipping depth is 1-5 cm, which can meet the requirements of most practical use processes.
According to some preferred embodiments, in the step S3, the mass ratio of the phenolic resin, the curing agent and the third solvent in the fourth impregnation liquid is 20 (1-5) to (80-120).
The fourth impregnation is to perform integral impregnation on the pretreated modified braided body after the local reinforcing impregnation so as to ensure that the phenolic resin can be uniformly distributed on the whole fiber braided body, and the composite material obtained after curing has higher strength and more stable structure.
According to some preferred embodiments, the temperature of the second pre-curing is 80 to 100 ℃ (e.g., may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃);
the curing is carried out for 5 to 30 hours (for example, 5 hours, 10 hours, 15 hours, 20 hours, 25 hours or 30 hours) at a temperature of between 150 and 180 ℃ (for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃); and/or the presence of a gas in the gas,
the temperature of the atmospheric drying is 170 to 190 ℃ (for example, 170 ℃, 175 ℃, 180 ℃, 185 ℃ or 190 ℃).
Firstly, pre-curing the impregnated pre-treated modified braided body at 80-100 ℃ to promote the curing and crosslinking formation of phenolic resin, and performing aging treatment at 150-180 ℃ to form a more complete structure; the purpose of drying is to remove the solvent remaining in the composite material after solvent displacement.
According to some preferred embodiments, the second solvent is one or more of absolute ethanol, acetone, toluene, n-hexane; the third solvent is one or more of absolute ethyl alcohol, deionized water, propanol, methanol and glycol; and/or the curing agent is one or more of paraformaldehyde, hexamethylenetetramine, aniline, formaldehyde and melamine.
The invention provides a modified high-temperature ablation-resistant heat-insulating composite material in a second aspect, which is prepared by the preparation method described above.
The density of the modified high-temperature ablation-resistant heat-insulating composite material prepared by the invention is 0.33-0.38 g/cm 3 The room temperature thermal conductivity is 0.17-0.23W/(mK), the thermal conductivity at 100 ℃ is 0.19-0.29W/(mK), and the residual weight after heating to 1300 ℃ in argon atmosphere is 81.9-83%; the modified high-temperature ablation-resistant heat-insulating composite material prepared by the invention has the advantages of low density, good heat resistance, low ablation rate, excellent ablation resistance and excellent oxidation resistance.
In order to more clearly illustrate the technical solutions and advantages of the present invention, the present invention is further described below with reference to the following embodiments.
The materials and the reagents in the invention can be obtained by direct purchase or self-synthesis on the market, and the specific model is not limited; the molar ratio of each acidic solution is the molar ratio of the solute.
The performance test methods of the examples and comparative examples of the present invention are as follows:
thermal conductivity at room temperature and thermal conductivity at 100 ℃: detecting according to the standard of GB/T3139-2005 test method for thermal conductivity coefficient of fiber reinforced plastics;
longitudinal compressive strength: the method is detected according to the standard of GB1448-2005 test method for compression property of fiber reinforced plastics.
Example 1
(1) Preparation of modified braid: mixing butyl titanate, absolute ethyl alcohol, deionized water, ethyl orthosilicate and methyltrimethoxysilane, then dropwise adding glacial acetic acid, and continuously stirring until the solution is close to gel to obtain a first impregnation solution; putting a continuous needling carbon fiber woven body with the size of 50cm multiplied by 3cm into a first impregnation liquid, then impregnating for 60min under the vacuum condition of 10kPa to ensure that the first impregnation liquid is completely filled with the fiber woven body, then transferring the fiber woven body into a polytetrafluoroethylene lining of a hydrothermal kettle, firstly gelling at 80 ℃, then aging for 3h at 120 ℃, then heating to 400 ℃ at the speed of 5 ℃/min in the air, and preserving heat for 2h to obtain a modified woven body; wherein, the molar ratio of butyl titanate, absolute ethyl alcohol, deionized water, ethyl orthosilicate, methyltrimethoxysilane and glacial acetic acid is 1;
(2) Pretreatment of the modified braided body: uniformly mixing phenolic resin and absolute ethyl alcohol according to a mass ratio of 20 2 Powder (the using amount is 5wt% of the phenolic resin) to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, impregnating for 60min under the vacuum condition of 5kPa, taking out, carrying out suction filtration, repeatedly impregnating for 3 times, and then heating for 10h at 120 ℃ to obtain a pretreated modified braided body;
(3) Preparing a modified high-temperature ablation-resistant heat-insulating composite material: uniformly mixing phenolic resin, hexamethylenetetramine and ethylene glycol according to a mass ratio of 20 2 Powder (5 wt% of phenolic resin) to obtain a third impregnation solution; uniformly mixing phenolic resin, hexamethylenetetramine and ethylene glycol according to a mass ratio of 20; firstly, dipping the pretreated modified braided body in a third dipping solution at 80 ℃, wherein the dipping depth is 5cm, and dipping is carried out for 30min under the vacuum condition of 10kPa; placing the soaked pretreated modified braided body in a fourth soaking solution, soaking for 60min under the vacuum condition of 10kPa, pre-curing at 100 ℃, and then curing for 5h at 180 ℃; and cooling, taking out, soaking in absolute ethyl alcohol, replacing the solution every 6 hours, replacing for 5 times, and drying at 190 ℃ to obtain the modified high-temperature ablation-resistant heat-insulating composite material.
The density of the modified high temperature ablation resistant thermal insulation composite material prepared in example 1 is about 0.36g/cm 3 The thermal conductivity at room temperature is 0.193W/mK, and the thermal conductivity at 100 ℃ is 0.216W/mK; the longitudinal compression strength is 9.82MPa, and the heat exchanger can be applied to a heat flow environment at 1900 ℃; FIG. 1 is a pictorial representation of the composite material obtained in example 1 before and after its ablation with oxyacetylene, showing non- (micro) ablation and good shape retention; as can be seen from fig. 5, the composite material obtained in example 1 has a dense surface; from FIG. 6It is known that the composite material obtained in example 1 had a residual weight of about 81.97% after heating to 1300 ℃ in an argon atmosphere.
Example 2
(1) Preparation of modified braid: mixing titanium isopropoxide, absolute ethyl alcohol, deionized water, ethyl orthosilicate and gamma-aminopropyltriethoxysilane, then dropwise adding hydrochloric acid, and continuously stirring until the solution is close to gel to obtain a first impregnation solution; placing the net tire quartz fiber woven body with the size of 30cm multiplied by 5cm into a first impregnation liquid, then impregnating for 30min under the vacuum condition of 5kPa to ensure that the fiber woven body is completely filled with the first impregnation liquid, then transferring to a polytetrafluoroethylene lining of a hydrothermal kettle, firstly gelling at 90 ℃, then aging for 4h at 120 ℃, then heating to 400 ℃ at the speed of 10 ℃/min in the air, and preserving heat for 1.5h to obtain a modified woven body; wherein, the molar ratio of titanium isopropoxide to absolute ethyl alcohol, deionized water to tetraethoxysilane, gamma-aminopropyltriethoxysilane to hydrogen chloride in hydrochloric acid is 1;
(2) Pretreatment of the modified braided body: uniformly mixing phenolic resin and toluene according to a mass ratio of 40 2 Powder (the dosage is 3wt% of the phenolic resin) to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, impregnating for 60min under normal pressure, taking out, carrying out suction filtration, repeatedly impregnating for 5 times, and then heating at 80 ℃ for 20h to obtain a pretreated modified braided body;
(3) Preparing a modified high-temperature ablation-resistant heat-insulating composite material: uniformly mixing phenolic resin, paraformaldehyde and methanol according to a mass ratio of 20 2 Powder (1 wt% of phenolic resin) to obtain a third impregnation solution; uniformly mixing phenolic resin, paraformaldehyde and methanol according to a mass ratio of 20; firstly, placing the pretreated modified braided body in a third impregnation process at 70 ℃, wherein the impregnation depth is 3cm, impregnating for 30min under normal pressure, then placing the pretreated modified braided body after impregnation in a fourth impregnation solution, and performing vacuum condition of 5kPa for 30min; then precuring at 90 ℃, and curing for 5 hours at 180 ℃; cooling, taking out, soaking in anhydrous ethanol,and replacing the solution every 6 hours, and drying at 190 ℃ after replacing for 3 times to obtain the modified high-temperature ablation-resistant heat-insulating composite material.
The density of the modified high temperature ablation resistant thermal insulation composite material prepared in example 2 is about 0.38g/cm 3 The thermal conductivity at room temperature is 0.176W/mK, and the thermal conductivity at 100 ℃ is 0.197W/mK; the longitudinal compression strength is 12.41MPa, and the heat exchanger can be applied to an environment with heat flow of 1800 ℃; as is clear from fig. 6, the residual weight of the composite material obtained in example 2 was about 82% after heating to 1300 ℃.
Example 3
(1) Preparation of modified braid: mixing titanium isopropoxide, absolute ethyl alcohol, deionized water, ethyl orthosilicate and dimethyl diethoxysilane, then dropwise adding nitric acid, and continuously stirring until the solution is close to gel to obtain a first impregnation solution; putting a three-dimensional woven mullite fiber woven body with the size of 60cm multiplied by 30cm multiplied by 10cm into a first impregnation liquid, then impregnating for 40min at normal pressure to enable the fiber woven body to be completely filled with the first impregnation liquid, then transferring to a polytetrafluoroethylene lining of a hydrothermal kettle, firstly gelling at 100 ℃, then aging for 3h at 120 ℃, then heating to 600 ℃ at the speed of 5 ℃/min under the protection of argon atmosphere, and preserving heat for 1.5h to obtain a modified woven body; wherein the molar ratio of titanium isopropoxide, anhydrous ethanol, deionized water, tetraethoxysilane, dimethyldiethoxysilane and nitric acid is 1;
(2) Pretreatment of the modified braided body: uniformly mixing phenolic resin and n-hexane according to the mass ratio of 40 2 Powder (the dosage is 1wt% of the phenolic resin) to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, impregnating for 30min under the vacuum condition of 10kPa, taking out, carrying out suction filtration, repeatedly impregnating for 3 times, and then heating for 20 hours at 100 ℃ to obtain a pretreated modified braided body;
(3) Preparing a modified high-temperature ablation-resistant heat-insulating composite material: uniformly mixing phenolic resin, formaldehyde and deionized water according to a mass ratio of 20 2 Powder (in an amount of 3wt% of the phenolic resin) to give a third impregnationLiquid; uniformly mixing phenolic resin, formaldehyde and deionized water according to a mass ratio of 20; firstly, dipping the pretreated modified braided body in a third dipping solution at the temperature of 80 ℃, wherein the dipping depth is 1cm, and dipping for 60min under the vacuum condition of 5 kPa; placing the soaked pretreated modified braided body in a fourth soaking solution, soaking for 60min at normal pressure, precuring at 100 ℃, and curing for 10h at 170 ℃; and cooling, taking out, soaking in absolute ethyl alcohol, replacing the solution every 4h for 5 times, and drying at 170 ℃ to obtain the modified high-temperature ablation-resistant heat-insulating composite material.
The density of the modified high temperature ablation resistant thermal insulation composite material prepared in example 3 is about 0.33g/cm 3 The thermal conductivity at room temperature is 0.229W/mK, the thermal conductivity at 100 ℃ is 0.287W/mK, the longitudinal compression strength is 14.36MPa, and the material can be applied to an environment with heat flow of 1800 ℃.
FIG. 2 is a pictorial representation of the composite material obtained in example 3 before and after its ablation with oxyacetylene, showing non- (micro) ablation and good shape retention; as can be seen from FIG. 7, the heat flow at peak is 1.5MW/m 2 The heat insulation material has the duration of 120s, the peak temperature of the surface is about 1400 ℃, the temperature rise of the back surface is 113.8 ℃, and the heat insulation property is good.
Comparative example 1
Uniformly mixing phenolic resin, hexamethylenetetramine and ethylene glycol according to a mass ratio of 20; placing the braid in the mixed solution, soaking for 60min under vacuum condition of 10kPa, firstly gelling at 100 ℃, and then aging for 5h at 180 ℃; cooling, taking out, soaking in anhydrous ethanol, replacing the solution every 6h for 5 times, and drying at 190 deg.C to obtain the heat-insulating composite material.
As can be seen from FIG. 6, the residual weight of the insulation composite prepared in comparative example 1 was 78.84%, and the thermal stability was significantly lower than that of example 1.
Comparative example 2
Comparative example 2 is essentially the same as example 1, except that: step (2) is omitted.
As shown in fig. 8, since the second impregnation liquid is not used for gap filling, cracks exist on the surface of the modified woven fabric, the surface of the finally prepared composite material is looser, and heat and oxygen are easy to invade, so that the oxidation resistance and ablation resistance of the material are reduced.
Comparative example 3
Comparative example 3 is essentially the same as example 1 except that: in the step (1), tetraethoxysilane and methyltrimethoxysilane are not added.
As shown in FIG. 9, due to TiO 2 Self-brittleness and lower chemical skeleton strength of the compound, resulting in TiO 2 The drying under atmospheric pressure results in extremely severe structural damage, which is then peeled off from the fiber surface during drying, so that a complete coating cannot be formed on the fiber surface, and finally no TiO can be obtained 2 An aerogel modified fiber preform.
Comparative example 4
Comparative example 4 is essentially the same as example 1 except that: in step (1), no butyl titanate was added.
Comparative example 4 No tetrabutyl titanate was added, and no rutile titanium dioxide functional phase with shielding infrared radiation existed on the surface of the composite material during ablation, resulting in a sharp increase in the surface temperature of the material and SiO of the material 2 Melting occurs, and the melted SiO is acted on by surface tension 2 A liquid film is formed on the surface of the material, and SiO is formed along with the prolonging of the ablation time 2 The surface tension of the liquid film cannot bear the action of gravity, so that overflow occurs, and the ablation rate of the material is increased.
Comparative example 5
Comparative example 5 is essentially the same as example 1, except that: in step (1), there is no heat treatment process.
Comparative example 5 since the sample was not heat-treated, the most predominant component of the oxidation-resistant coating coated on the surface of the material was amorphous TiO 2 And SiO 2 (ii) a Due to SiO 2 In the presence of, tiO 2 The crystal form transformation can occur only by higher energy, so that the infrared radiation shielding performance of the composite material prepared without heat treatment in the same environment is poorer, the surface temperature of a sample is higher, and the ablation resistance protection of the composite material in a high-temperature and high-radiation environment is not facilitated.
It should be noted that in the description of the embodiments of the present invention, unless explicitly stated or limited otherwise, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a modified high-temperature ablation-resistant heat-insulation composite material is characterized by comprising the following steps:
s1, mixing a titanium dioxide precursor, a silicon dioxide precursor, a silane coupling agent, a first solvent and an acidic solution to obtain a first impregnation liquid, placing a fiber woven body into the first impregnation liquid, and performing first impregnation, gelation treatment, aging treatment and heat treatment to obtain a modified woven body;
s2, mixing phenolic resin, nano titanium dioxide and a second solvent to obtain a second impregnation liquid, placing the modified braided body in the second impregnation liquid, and performing second impregnation and first precuring to obtain a pretreated modified braided body;
s3, carrying out third impregnation, fourth impregnation, second precuring, curing, solvent replacement and normal-pressure drying on the pretreated modified braided body to obtain a modified high-temperature ablation-resistant heat-insulation composite material; the third impregnation liquid for carrying out the third impregnation is obtained by mixing phenolic resin, a curing agent, nano titanium dioxide and a third solvent; and the fourth impregnation liquid for performing the fourth impregnation is obtained by mixing phenolic resin, a curing agent and a third solvent.
2. The method according to claim 1, wherein in step S1, the molar ratio of the titania precursor, the silica precursor, the silane coupling agent, the first solvent, and the solute in the acidic solution is 1 (0-1): 21-42: (1-4), wherein the mole numbers of the silica precursor and the silane coupling agent are not 0 at the same time.
3. The method according to claim 1, wherein in step S1, the titanium dioxide precursor is selected from one or more of butyl titanate, titanium isopropoxide, and titanium butoxide;
the silicon dioxide precursor is tetraethoxysilane;
the silane coupling agent is selected from one or more of methyltrimethoxysilane, dimethyldiethoxysilane, gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane;
the first solvent is ethanol solution; preferably, the molar ratio of the ethanol to the water in the first solvent is (18-36) to (3-6); and/or
The acid solution is one or more of glacial acetic acid, hydrochloric acid and nitric acid.
4. The production method according to claim 1, wherein in step S1, the fiber woven body is made of carbon fiber, quartz fiber, glass fiber, or mullite fiber; preferably, the fiber knitted body is a continuous fiber needle punched structure, a net tire structure, a 2.5D knitted structure or a three-dimensional knitted structure; more preferably, the fiber woven body has a length of 30. + -.10 cm, a width of 30. + -.10 cm and a thickness of 10. + -.5 cm.
5. The method according to claim 1, wherein the temperature of the gelation process is 80 to 100 ℃ in step S1;
the temperature of the aging treatment is 100-120 ℃, and the time is 3-6 h; and/or
The heat treatment is to heat up to 400-600 ℃ at the heating rate of 4-10 ℃/min and keep the temperature for 1.5-3.5 h.
6. The preparation method according to claim 1, wherein in step S2, the mass ratio of the phenolic resin, the nano titanium dioxide and the second solvent in the second impregnation solution is (20-40): (0.2-2): (100-120);
the first pre-curing is heat preservation for 10 to 20 hours at a temperature of between 100 and 120 ℃.
7. The preparation method according to claim 1, wherein in step S3, the mass ratio of the phenolic resin, the nano titanium dioxide, the curing agent and the third solvent in the third impregnation solution is 20 (0.2-1): 1-5: 80-120);
the temperature of the third impregnation is 70-80 ℃, and the time is 30-60 min; preferably, the third impregnation is performed to an impregnation depth of 1 to 5cm.
8. The preparation method according to claim 1, wherein in step S3, the mass ratio of the phenolic resin, the curing agent and the third solvent in the fourth impregnation liquid is 20 (1-5) to (80-120);
the temperature of the second precuring is 80-100 ℃;
the curing is carried out for 5 to 30 hours at the temperature of between 150 and 180 ℃; and/or
The temperature of the normal pressure drying is 170-190 ℃.
9. The preparation method according to claim 1, wherein the second solvent is one or more of absolute ethyl alcohol, acetone, toluene and n-hexane;
the third solvent is one or more of absolute ethyl alcohol, deionized water, propanol, methanol and glycol; and/or
The curing agent is one or more of paraformaldehyde, hexamethylenetetramine, aniline, formaldehyde and melamine.
10. A modified high-temperature ablation-resistant heat-insulating composite material, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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