Ablative-resistant coating and its preparation method and application

Abstract

The application discloses a kind of ablation-resistant paint and its preparation method and application, belong to coating technical field.The application is by synthesizing P-Si with Si-O-Si crosslinking structure, processing proportionally mixed expandable graphite, silicon carbide, zirconium carbide, ammonium polyphosphate raw material solid powder, both are mixed with ceramic fiber at 140~150 ℃ temperature proportionally, P-Si with Si-O-Si crosslinking structure is mixed with expandable graphite, silicon carbide, zirconium carbide, ammonium polyphosphate compound proportionally by modification, in long chain structure gamma-glycidyl ether oxypropyl trimethoxysilane and branched chain structure tetramethoxysilane, heat extension in long chain direction is retained, and is subjected to steric effect of branched structure simultaneously;By optimizing the proportion of P-Si with Si-O-Si crosslinking structure and treated inorganic filler, the effect of both is balanced, and the coating stability under high temperature is improved.In addition, the adhesion of treated inorganic filler is enhanced by activation, and the ablation-resistant temperature and wear coefficient of ablation-resistant paint are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the paint technology, specifically relates to a kind of ablation-resistant paint and its preparation method and application. BACKGROUND

[0002] The fast sampling tool with good ablation-resistant paint coating is the key component of ablation test equipment, and plays a crucial role in realizing fast sampling and protecting ablation test equipment. The traditional ablation-resistant coating often leads to the strength and effect of the coating to decline after several hundred times of ablation-resistant sampling friction. SUMMARY

[0003] The technical problem to be solved by the present application is to provide an ablation-resistant paint with high ablation-resistant temperature and wear coefficient, and its preparation and application.

[0004] To solve the above technical problems, the technical solution adopted by the present application is as follows: by synthesizing P-Si with Si-O-Si crosslinking structure, treating the proportionally mixed expandable graphite, silicon carbide, zirconium carbide and ammonium polyphosphate raw solid powder, and mixing the two with ceramic fiber at a proportion at a temperature of 140℃~150℃, an ablation-resistant paint is prepared, which is applied to the wall of metal or ceramic pipe, can effectively improve the ablation-resistant temperature and wear coefficient of the pipe wall, thereby achieving the purpose of the present application.

[0005] The present application relates to a preparation method of an ablation-resistant paint, and the preparation steps are as follows:

[0006] 1) Synthesis of P-Si with Si-O-Si crosslinking structure

[0007] Add tetramethoxysilane and γ-glycidyl ether propyltrimethoxysilane with a mass ratio of 1:(4~6) to tetrahydrofuran, with a material-liquid ratio of (50~70)g:200mL; under nitrogen protection, stir and heat to 80℃~100℃, continue to react for 6h~10h, then stop stirring; continue to cool to room temperature under nitrogen protection to obtain polysilane filler P-Si with Si-O-Si crosslinking structure, and its structural formula is as follows:

[0008]

[0009] 2) Treatment of inorganic fillers

[0010] Mixing expandable graphite, silicon carbide, zirconium carbide, ammonium polyphosphate raw material solid powder with mass ratio (1~1.1):(1~1.1):(3~3.2):(0.5~0.7) uniformly, then adding into tetramethoxysilane, wherein the ratio of material to liquid is (55~57)g:(200~250)mL, fully stirring at 140℃~150℃ temperature, then centrifugal processing, taking the lower layer product after processing and fully stirring with γ-glycidyl ether propyl trimethoxysilane at 130℃~140℃ temperature, wherein the ratio of material to liquid is 100g:(200~250)mL, then centrifugal processing again, taking the lower layer product after centrifugal processing and grinding to obtain the treated inorganic filler;

[0011] 3) Preparation of the ablation-resistant coating

[0012] Mixing the treated inorganic filler with P-Si having Si-O-Si crosslinking structure for not less than 10h at 140℃~150℃ temperature, then adding ceramic fiber and continuing mixing for not less than 5h to obtain the ablation-resistant coating, wherein the mass ratio of the treated inorganic filler, P-Si having Si-O-Si crosslinking structure and ceramic fiber is (2~20):(1~9):(2~20).

[0013] Preferably, in the treatment of inorganic filler in step 2), the particle size of expandable graphite, silicon carbide, zirconium carbide and ammonium polyphosphate is 10μm~100μm, and the mass ratio is 1:1:3:(0.5~0.7).

[0014] Preferably, in the treatment of inorganic filler in step 2), the particle size of the treated inorganic filler is 10μm~100μm.

[0015] Preferably, in the treatment of inorganic filler in step 2), the centrifugal processing operation is not less than 20min.

[0016] Preferably, in the preparation of ablation-resistant coating in step 3), the diameter of ceramic fiber is 2μm~5μm.

[0017] The application also relates to an ablation-resistant coating, which is prepared by mixing the treated inorganic filler, P-Si having Si-O-Si crosslinking structure and ceramic fiber with mass ratio (2~20):(1~9):(2~20).

[0018] The application also relates to the application of the ablation-resistant coating, which is applied to the wall of metal or ceramic pipe and solidified to obtain an ablation-resistant coating.

[0019] Preferably, the wall is the inner wall of the ablation test sample delivery pipe.

[0020] Preferably, the ablation-resistant coating is applied to the pipe wall with a thickness of 2mm to 6mm.

[0021] The application relates to a preparation method of an ablation-resistant coating, which comprises the following steps: synthesizing P-Si with a Si-O-Si crosslinking structure, processing solid powder of expandable graphite, silicon carbide, zirconium carbide and ammonium polyphosphate which are mixed in proportion, mixing the processed inorganic fillers and ceramic fibers in proportion at a temperature of 140 DEG C to 150 DEG C, and retaining the heat extension in the long chain direction of long-chain structure gamma-glycidoxypropyltrimethoxysilane and branched structure tetramethoxysilane by modifying the P-Si with the Si-O-Si crosslinking structure and the expandable graphite, silicon carbide, zirconium carbide and ammonium polyphosphate compound in proportion, balancing the effects of the P-Si with the Si-O-Si crosslinking structure and the processed inorganic fillers by optimizing the proportion of the P-Si with the Si-O-Si crosslinking structure and the processed inorganic fillers, and improving the coating stability at high temperature. In addition, the adhesion of the processed inorganic fillers is enhanced by the activation of the silane polymer with the Si-O-Si crosslinking structure, and the ablation-resistant temperature and the wear coefficient of the ablation-resistant coating are improved. DETAILED DESCRIPTION

[0022] The detailed description of the application is used to provide the necessary disclosure for the person skilled in the art to fully understand the application, and aims to effectively support the claims of the application. Meanwhile, the part will involve the explanation or definition of the features and terms of the technical scheme of the application, and the person skilled in the art should understand the limited range of the claims of the application in combination with the explanation of the specific features and terms in the specification, and should not arbitrarily distort the true connotation represented by the features and terms of the application.

[0023] It must be understood that, in any definition work related to the scope of the claims of the application, the specific embodiments provided by the application can fully support the general or superior suitable scheme generalization induced thereby, and the scope of the claims should never be understood beyond the examples themselves. It must also be understood that, with the development of technology and the appearance of new scenarios, the technical scheme provided by the embodiments of the application will also be applicable to similar technical problems within the range of no creative labor of the person skilled in the art, and the protection scope of the application should not be limited in the examples recorded in the detailed description of the application.

[0024] Embodiment 1

[0025] The ablation-resistant coating of the embodiment is mixed by the processed inorganic fillers, the P-Si with the Si-O-Si crosslinking structure and the ceramic fibers in a mass ratio of 2:1:2, and the preparation method is as follows:

[0026] 1 Synthesis of P-Si with Si-O-Si crosslinking structure

[0027] 10g tetramethoxysilane and 60g γ-glycidoxypropyltrimethoxysilane were added to 200mL of tetrahydrofuran, stirred at 400rpm under nitrogen protective gas and heated to 100℃, the stirring was stopped after 10h of continuous reaction; then, continue to cool to room temperature under nitrogen protective gas to obtain polysilane filler P-Si with Si-O-Si cross-linked structure. The chemical formula of P-Si is as follows:

[0028]

[0029] 2 Treatment of inorganic fillers

[0030] The expandable graphite with a particle size of 10μm, silicon carbide with a particle size of 20μm, zirconium carbide with a particle size of 15μm and ammonium polyphosphate solid powder with a particle size of 10μm in a mass ratio of 1:1:3:0.7 were mixed, stirred for 1h to make them uniformly mixed, then added to 200mL of tetramethoxysilane, fully stirred at 150℃ for 5h, and then centrifuged for 20min. The lower layer product after centrifugation was taken out, 100g of which was mixed with 200mL of γ-glycidoxypropyltrimethoxysilane at 140℃ for 10h of full stirring, and then centrifuged for 20min. The lower layer product after centrifugation was ground to 10μm to obtain the treated inorganic filler.

[0031] 3 Preparation of ablation-resistant coating

[0032] At 150℃, 100g of the treated inorganic filler was stirred with 50g of P-Si for 10h, then 100g of ceramic fiber with a diameter of 2μm was added, and the stirring was continued for 5h to obtain the ablation-resistant coating, which was sealed and stored in the dark.

[0033] The ablation-resistant coating prepared in this example was tested for wear resistance after being coated to a thickness of 2mm according to GB / T 17657-2022, and the test results were as follows:

[0034] 1. Ablation-resistant temperature of 1850℃;

[0035] 2. Wear resistance at 1400℃ high temperature: wear value of 1g / 100r;

[0036] 3. Mass loss rate <0.1% after 500 times of rapid sample loading at 1500℃ high temperature.

[0037] Example 2

[0038] The ablation-resistant coating of this example was prepared by mixing the treated inorganic filler, P-Si with Si-O-Si cross-linked structure and ceramic fiber in a mass ratio of 5:2:5, and the preparation method was as follows:

[0039] 1. Synthesis of P-Si with Si-O-Si cross-linked structure

[0040] Into 200 mL of tetrahydrofuran, 10 g of tetramethoxysilane and 53 g of γ-glycidoxypropyltrimethoxysilane were added, stirred at a speed of 400 revolutions per minute under nitrogen protective gas and at the same time heated to 87℃, and after 7 h of continuous reaction, the stirring was stopped; then, under nitrogen protective gas, cooling to room temperature was continued to obtain a polysilane filler P-Si.

[0041] 2 Treatment of inorganic fillers

[0042] 56 g of expandable graphite with a particle size of 100 μm, silicon carbide with a particle size of 80 μm, zirconium carbide with a particle size of 100 μm and ammonium polyphosphate solid powder with a particle size of 90 μm in a mass ratio of 1:1:3:0.6 were mixed, stirred for 2 h to make them uniformly mixed, then added into 250 mL of tetramethoxysilane, fully stirred at 140℃ for 7 h, and then centrifuged for 30 min. 100 g of the lower layer product after centrifugation was mixed with 250 mL of γ-glycidoxypropyltrimethoxysilane at 130℃ for 12 h of full stirring, and then centrifuged for 30 min. The lower layer product after centrifugation was ground to 100 μm to obtain a treated inorganic filler.

[0043] 3 Preparation of ablation-resistant coating

[0044] 100 g of the inorganic filler was mixed with 40 g of P-Si at 140℃ for 12 h, then 100 g of ceramic fiber with a diameter of 5 μm was added, and the stirring was continued for 6 h to obtain an ablation-resistant coating slurry, which was sealed and stored in the dark.

[0045] The ablation-resistant coating prepared in this example was tested for wear resistance after being coated to a thickness of 2 mm according to GB / T 17657-2022, and the test results were as follows:

[0046] 1. Ablation-resistant temperature of 1700℃;

[0047] 2. Wear resistance at 1400℃ high temperature: wear value of 1.5 g / 100r;

[0048] 3. Mass loss rate <0.1% after 500 times of rapid sample loading at 1500℃ high temperature.

[0049] Example 3

[0050] The ablation-resistant coating of this example was prepared by mixing treated inorganic fillers, P-Si with Si-O-Si crosslinking structure and ceramic fiber in a mass ratio of 20:9:20, and the preparation method was as follows:

[0051] 1. Synthesis of P-Si with Si-O-Si crosslinking structure:

[0052] 10 g tetramethoxysilane and 40 g γ-glycidoxypropyltrimethoxysilane were added to 200 mL of tetrahydrofuran, stirred at a speed of 400 revolutions per minute under nitrogen protective gas and at the same time heated to 80°C, and after 6 h of reaction, the stirring was stopped; then, under nitrogen protective gas, the cooling to room temperature was continued to obtain a liquid polysilane filler P-Si.

[0053] 2 Treatment of inorganic fillers

[0054] 55 g of expandable graphite with a particle size of 50 μm, silicon carbide with a particle size of 60 μm, zirconium carbide with a particle size of 55 μm and ammonium polyphosphate powder with a particle size of 70 μm in a mass ratio of 1:1:3:0.5 were mixed, stirred for 1.5 h to make them uniformly mixed, then added to 200 mL of tetramethoxysilane, stirred at 150°C for 6 h, and then centrifuged for 30 min. 100 g of the lower layer product after centrifugation was mixed with 200 mL of γ-glycidoxypropyltrimethoxysilane at 140°C and stirred for 10 h, and then centrifuged for 30 min. The lower layer product after centrifugation was ground to 50 μm to obtain a treated inorganic filler.

[0055] 3 Preparation of ablation-resistant coating

[0056] 100 g of inorganic filler was stirred in 45 g of P-Si at 150°C for 12 h, then 100 g of ceramic fiber was added and stirred for another 5 h to obtain an ablation-resistant coating slurry, which was sealed and stored in the dark.

[0057] The ablation-resistant coating prepared in this example was coated to a thickness of 2 mm according to GB / T 17657-2022, and the wear resistance test was performed, and the test results were as follows:

[0058] 1. Ablation-resistant temperature 1670°C;

[0059] 2. Wear resistance at 1400°C high temperature: wear value 1.6 g / 100r;

[0060] 3. Mass loss rate <0.1% after 500 times of rapid sample loading at 1500°C high temperature.

[0061] Comparative Example 1

[0062] The difference from Example 3 is that:

[0063] The ablation-resistant coating was prepared by mixing treated inorganic fillers and ceramic fibers in a mass ratio of 11:20, and the preparation method was as follows:

[0064] The expandable graphite, silicon carbide, zirconium carbide, and ammonium polyphosphate powder with a mass ratio of 1:1:3:0.5 were uniformly mixed, and then added to 200 mL of tetramethoxysilane. The mixture was stirred at 150°C for 6 hours, then centrifuged for 30 minutes. The lower layer product after centrifugation was taken out, and 100 g of the product was mixed with 200 mL of γ-glycidoxypropyltrimethoxysilane at 140°C for 10 hours, then centrifuged for 30 minutes. The lower layer product after centrifugation was taken out and ground to 10 μm to obtain a treated inorganic filler. Then 100 g of ceramic fiber was added and stirred for 5 hours to obtain a slurry which was sealed and stored in dark light.

[0065] The ablation-resistant coating prepared in this example was coated to a thickness of 2 mm according to GB / T 17657-2022, and then subjected to wear resistance test. The test results were as follows:

[0066] 1. Ablation-resistant temperature of 740°C;

[0067] 2. Wear resistance at 1400°C high temperature: wear value: 2.1 g / 100r;

[0068] 3. Mass loss rate <0.27% after 500 times of rapid sample loading at 1500°C high temperature.

[0069] Comparative Example 2

[0070] The difference from Example 2 is that:

[0071] The ablation-resistant coating was prepared by mixing P-Si with Si-O-Si cross-linked structure and untreated inorganic filler with a mass ratio of 5:2. The preparation method is as follows:

[0072] 1. Synthesis of P-Si with Si-O-Si cross-linked structure

[0073] 10 g of tetramethoxysilane and 53 g of γ-glycidoxypropyltrimethoxysilane were added to 200 mL of tetrahydrofuran, and stirring was started under nitrogen protection gas while the temperature was raised to 87°C. After 7 hours of reaction, the stirring was stopped, and the stirring speed was 400 revolutions per minute. The mixture was then cooled to room temperature (25°C) under nitrogen protection gas to obtain polysilane P-Si with Si-O-Si cross-linked structure.

[0074] 2. Preparation of ablation-resistant coating

[0075] Expandable graphite, silicon carbide, zirconium carbide, and ammonium polyphosphate powder with a mass ratio of 1:1:3:0.6 were uniformly mixed, and then added to 40 g of P-Si and stirred at 140°C for 12 hours. Then 100 g of ceramic fiber was added and stirred for 6 hours to obtain a slurry which was sealed and stored in dark light.

[0076] The ablation-resistant coating prepared in this example was coated to a thickness of 2 mm according to GB / T 17657-2022, and then subjected to wear resistance test, and the test result was:

[0077] 1. Ablation-resistant temperature 1170℃;

[0078] 2. Wear resistance at 1400℃ high temperature: wear value 1.8g / 100r;

[0079] 3. Mass loss rate <0.13% after 500 times of rapid sample loading at 1500℃ high temperature.

[0080] Comparative Example 3

[0081] The difference from Example 2 is that:

[0082] The ablation-resistant coating is mixed from treated inorganic fillers and ceramic fibers with a mass ratio of 1:1, and the preparation method is as follows:

[0083] Mix 56g of expandable graphite, silicon carbide, zirconium carbide and ammonium polyphosphate powder with a mass ratio of 1:1:3:0.6, then add to 250mL tetramethoxysilane, stir at 140℃ for 7h, then centrifuge for 30min, take 100g of the lower layer product after centrifugation and grind to 100μm, which is the treated inorganic filler; then add 100g of ceramic fiber, continue to stir for 6h to obtain a slurry, and store in sealed dark place.

[0084] The ablation-resistant coating prepared in this example was coated to a thickness of 2 mm according to GB / T 17657-2022, and then subjected to wear resistance test, and the test result was:

[0085] 1. Ablation-resistant temperature 550℃;

[0086] 2. Wear resistance at 1400℃ high temperature: wear value 1.64g / 100r;

[0087] 3. Mass loss rate <0.38% after 500 times of rapid sample loading at 1500℃ high temperature.

[0088] Comparative Example 4

[0089] The difference from Example 2 is that:

[0090] The ablation-resistant coating is mixed from treated inorganic fillers and ceramic fibers with a mass ratio of 1:1, and the preparation method is as follows:

[0091] 56g of expandable graphite, silicon carbide, zirconium carbide, and ammonium polyphosphate powder in a mass ratio of 1:1:3:0.6 were mixed evenly, and then 80g of γ-glycidoxypropyltrimethoxysilane was stirred at 130℃ for 12h. After centrifugation for 30min, 100g of the lower layer product after centrifugation was taken and ground to 100μm to obtain the treated inorganic filler. Then 100g of ceramic fiber was added and stirring was continued for 6h to obtain a slurry, which was then sealed and stored in the dark.

[0092] Performance testing:

[0093] 1. Ablation resistance temperature: 570 ℃;

[0094] 2. Wear resistance at 1400℃: Wear value: 1.61g / r;

[0095] 3. The mass loss rate after 500 rapid sample loading cycles at 1500℃ is <0.41%.

[0096] Application examples

[0097] The slurries prepared in Examples 1-3 are applied to the inner wall of the ablation test sample delivery pipe made of metal or ceramic with a thickness of 2 mm to 6 mm. After static curing, an ablation-resistant coating is obtained, which gives the pipe wall ablation resistance and durability.

Claims

1. A method for preparing an ablation-resistant coating, characterized in that, The preparation steps are as follows: 1) Synthesis of P-Si with Si-O-Si crosslinking structure Tetramethoxysilane and γ-glycidoxypropyltrimethoxysilane in a mass ratio of 1:(4~6) were added to tetrahydrofuran, with a material-to-liquid ratio of (50~70) g:200 mL. Under nitrogen protection, the mixture was stirred and heated to 80℃~100℃, and the reaction was continued for 6h~10h before stirring was stopped. The mixture was then cooled to room temperature under nitrogen protection to obtain the polysilane filler P-Si with a Si-O-Si crosslinked structure, the structural formula of which is as follows: 2) Treatment of inorganic packing materials Expandable graphite, silicon carbide, zirconium carbide, and ammonium polyphosphate raw material solid powders in a mass ratio of (1~1.1):(1~1.1):(3~3.2):(0.5~0.7) were mixed evenly and then added to tetramethoxysilane, with a material-to-liquid ratio of (55~57)g:(200~250)mL. The mixture was stirred thoroughly at 140℃~150℃ and then centrifuged. The lower layer of the treated product was taken and stirred thoroughly with γ-glycidoxypropyltrimethoxysilane at 130℃~140℃, with a material-to-liquid ratio of 100g:(200~250)mL. The mixture was then centrifuged again. The lower layer of the centrifuged product was ground to obtain the treated inorganic filler. 3) Preparation of ablation-resistant coatings At a temperature of 140℃~150℃, the treated inorganic filler and P-Si with Si-O-Si cross-linking structure are mixed and stirred for no less than 10h, and then ceramic fibers are added and the mixture is stirred for no less than 5h to obtain the ablation resistant coating. The mass ratio of the treated inorganic filler, P-Si with Si-O-Si cross-linking structure and ceramic fibers is (2~20):(1~9):(2~20).

2. The method for preparing an ablation-resistant coating according to claim 1, characterized in that: In step 2), during the treatment of inorganic fillers, the particle size of the expandable graphite, silicon carbide, zirconium carbide, and ammonium polyphosphate is 10 μm to 100 μm, and the mass ratio is 1:1:3:(0.5~0.7).

3. The method for preparing an ablation-resistant coating according to claim 1, characterized in that: In step 2), the particle size of the treated inorganic filler is 10 μm to 100 μm.

4. The method for preparing an ablation-resistant coating according to claim 1, characterized in that: Step 2) In the treatment of inorganic packing materials, the centrifugation operation shall not be less than 20 minutes.

5. The method for preparing an ablation-resistant coating according to claim 1, characterized in that: In step 3) the preparation of the ablation-resistant coating, the diameter of the ceramic fiber is 2μm~5μm.

6. The ablation-resistant coating prepared by the method for preparing an ablation-resistant coating according to any one of claims 1 to 5, characterized in that: It is composed of treated inorganic fillers in a mass ratio of (2~20):(1~9):(2~20), P-Si with Si-O-Si cross-linked structure and ceramic fibers.

7. The application of the ablation-resistant coating according to claim 6, characterized in that: The ablation-resistant coating is obtained by applying the ablation-resistant coating to the wall of a metal or ceramic pipe and then allowing it to cure.

8. The application of the ablation-resistant coating according to claim 7, characterized in that: The pipe wall is the inner wall of the ablation test sample delivery pipe.

9. The application of the ablation-resistant coating according to claim 7, characterized in that: The ablation-resistant coating is applied to the pipe wall at a thickness of 2mm to 6mm.

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