Carbon fiber-ultra high temperature ceramic composite material and preparation method thereof

Abstract

This invention discloses a carbon fiber-ultra-high temperature ceramic composite material and its preparation method. (1) Mix 1# liquid resin and copper powder and adjust the viscosity of the slurry to obtain precursor A; (2) Impregnate precursor A into carbon fiber preform and pyrolyze to obtain intermediate B; (3) Mix 2# liquid resin and ultra-high temperature ceramic particles and adjust the viscosity of the slurry to obtain precursor C; (4) Impregnate precursor C into intermediate B using the PIP method, then cure and vacuum pyrolyze to obtain intermediate D1; (5) Replace intermediate B with intermediate D1 and repeat steps (3)-(4) to obtain intermediate D2; and so on, until intermediate D is obtained. n (6) For intermediate D n (7) The precursor C is impregnated into the porous intermediate E by heat treatment to remove copper, and then pyrolyzed to obtain the carbon fiber-ultra-high temperature ceramic composite material. The composite material prepared by this invention has a high ultra-high temperature ceramic content and good high temperature resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of composite materials, and particularly relates to a carbon fiber-ultra-high-temperature ceramic composite material and a preparation method thereof. BACKGROUND

[0002] The hot end part of a hypersonic vehicle often has to withstand extreme service environment, and the flight speed of the vehicle is generally above 5 Mach, so that the high-temperature resistance, oxidation corrosion resistance of the hot end part and the strength and toughness of the structural material have high requirements. The currently used materials cannot meet the long-time flight of the hypersonic vehicle due to their weak oxidation resistance and low material toughness, thereby limiting the application scenarios.

[0003] The introduction of ultra-high-temperature ceramics into the carbon-carbon composite material matrix to prepare a carbon fiber-ultra-high-temperature ceramic composite material can improve the oxidation resistance and ablation resistance of the carbon-carbon composite material and improve the use temperature of the material. The carbon fiber-ultra-high-temperature ceramic composite material represented by ZrC, TaC and HfC has become a research hotspot. However, the carbon fiber-ultra-high-temperature ceramic composite material prepared by the current process has the problem of low content of ultra-high-temperature ceramics, so that the high-temperature resistance is not ideal. SUMMARY

[0004] In order to overcome the deficiencies in the prior art, the present application aims to provide a carbon fiber-ultra-high-temperature ceramic composite material and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a carbon fiber-ultra-high-temperature ceramic composite material, the preparation steps being as follows:

[0007] (1) 1# liquid resin and copper powder are uniformly mixed in a mass ratio of 1:(0.01-0.5), and 1# diluent is added thereto to adjust the viscosity of the slurry until the viscosity measured by the Zahn cup method is 100 mL slurry flow-out time of 20-70 s, to obtain a precursor A;

[0008] (2) The precursor A is impregnated into a carbon fiber preform, and pyrolysis is carried out at 900-1100 DEG C under vacuum for 1-3 h to obtain an intermediate B;

[0009] (3) 2# liquid resin and ultra-high-temperature ceramic particles are uniformly mixed in a mass ratio of 1:(0.01-0.5), and 2# diluent is added thereto to adjust the viscosity of the slurry until the viscosity measured by the Zahn cup method is 100 mL slurry flow-out time of 20-70 s, to obtain a precursor C;

[0010] (4) The precursor C is first impregnated into intermediate B using the PIP method, then cured at 150~200 ℃ for 2~5 h, and finally pyrolyzed under vacuum at 900~1000 ℃ for 1~3 h to obtain intermediate D1.

[0011] (5) Replace intermediate B with intermediate D1 and repeat steps (3)-(4) to obtain intermediate D2; then replace intermediate B with intermediate D2 and repeat steps (3)-(4) to obtain intermediate D3; and so on, repeating steps (3)-(4) until intermediate D is obtained. n n≥2 and intermediate D n With intermediate D n-1 Compared to a weight gain rate of less than 2%;

[0012] (6) For intermediate D n Except for Cu: at 1200~1800 ℃, for intermediate D n Heat treatment for 2-4 hours yields porous intermediate E;

[0013] (7) Impregnate the precursor C into the porous intermediate E and pyrolyze it at 900~1000 ℃ for 2~4 h to obtain carbon fiber-ultra-high temperature ceramic composite material.

[0014] Preferably, the copper powder has a particle size of 1~5μm.

[0015] Preferably, the density of the carbon fiber preform is 0.5~0.8 g / cm³. 3 At this carbon fiber preform density, Cu in precursor A can smoothly enter the interior of the carbon fiber preform.

[0016] Ideally, the particle size of the ultra-high temperature ceramic particles is 50 ~ 1000 nm.

[0017] Preferably, the ultra-high temperature ceramic particles are one or a mixture of several of ZrC, TaC, and HfC.

[0018] Preferably, liquid resin #1 and liquid resin #2 are the same, selected from one or a mixture of several of phenolic resin, benzoxazine resin, furan resin, polyurea, and phenolic modified epoxy resin.

[0019] Preferably, the furan resin is a furfuryl ketone resin.

[0020] Preferably, the No. 1 diluent and the No. 2 diluent are the same, selected from one or a mixture of several of ethanol, toluene, dioctyl phthalate, dibutyl phthalate, and triethyl phosphate.

[0021] Preferably, in steps (1) and (3), the mass ratio of 1# liquid resin to copper powder is 1: (0.05-0.2), and the mass ratio of 2# liquid resin to ultra-high temperature ceramic particles is 1: (0.05-0.2), and the viscosity of 100 mL slurry measured by the Zhan cup method is 30-50 s.

[0022] A carbon fiber-ultra-high temperature ceramic composite material prepared by the preparation method.

[0023] In the present application, steps (1) and (3) use the Zhan cup method to adjust the slurry to the required viscosity, so that the slurry fully enters the carbon fiber preform or the intermediate body. If the slurry is too viscous, it will increase the difficulty of impregnation, and if it is too thin, it will leave many pores after pyrolysis, which will result in the final prepared composite material having too low density and not having high temperature resistance. The ultra-high temperature ceramic is mixed with the resin, and enters the intermediate body by PIP method (impregnation-curing-pyrolysis) to form an intermediate body D containing ultra-high temperature ceramic n However, the melting point of copper is 1083.4 ℃, which will melt at high temperature, affecting the temperature resistance of the composite material, so it is necessary to remove the copper from the intermediate body D n

[0024] The reason is that, on the one hand, if pure resin precursor enters the carbon fiber preform, it will fill the carbon fiber preform too much, resulting in the ultra-high temperature ceramic being unable to enter the intermediate body, and on the other hand, when using a mixture of resin and ultra-high temperature ceramic particles as a precursor, the ultra-high temperature ceramic particles often stop impregnating after maintaining a certain proportion with the carbon fiber, and the present application uses copper powder to create pores, which can provide sufficient channels for the subsequent addition of ultra-high temperature ceramic particles, and the intermediate body D n After the copper melt seeps out, the intermediate body E with pores is formed, the precursor C is impregnated again, and the ultra-high temperature ceramic enters the pores, solving the problem that the ultra-high temperature ceramic particles are difficult to enter the intermediate body and resulting in the final prepared composite material having a low content of ultra-high temperature ceramic.

[0025] Beneficial effects: the carbon fiber-ultra-high temperature ceramic composite material prepared by the copper powder pore-making method of the present application has a high content of ultra-high temperature ceramic and good high temperature resistance, and can support the extreme environmental service behavior of hypersonic aircraft. DETAILED DESCRIPTION

[0026] To make the present application clearer and more explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0027] Example 1

[0028] A preparation method of a carbon fiber-ultra-high temperature ceramic composite material, the preparation steps are as follows:

[0029] (1) 1# resin, copper powder (particle size 1 μm) were mixed uniformly according to the mass ratio of 1:0.2, and 1# diluent was added to adjust the slurry viscosity, until the viscosity was 100 mL slurry outflow time was 25 s measured by the cup method, to obtain precursor A; wherein, 1# resin is 2127 phenolic resin, 1# diluent is anhydrous ethanol;

[0030] (2) The precursor A was impregnated into the carbon fiber preform with a density of 0.65 g / cm 3 , and pyrolysis was carried out at 1100 ℃ under vacuum for 1 h to obtain intermediate B;

[0031] (3) 2# resin and ultra-high temperature ceramic particles (particle size 500 nm) were mixed uniformly according to the mass ratio of 1:0.2, and 2# diluent was added to adjust the slurry viscosity, until the viscosity was 100 mL slurry outflow time was 25 s measured by the cup method, to obtain precursor C; wherein, 2# resin is 2127 phenolic resin; 1# diluent is anhydrous ethanol; the ultra-high temperature ceramic particles are ZrC and TaC mixed in equal mass ratio;

[0032] (4) The precursor C was impregnated into the intermediate B by PIP method, then cured at 180 ℃ for 4 h, and finally pyrolyzed at 1000 ℃ under vacuum for 2 h to obtain intermediate D1;

[0033] (5) The intermediate D1 was replaced by the intermediate B, and steps (3)-(4) were repeated to obtain the intermediate D2; the intermediate D2 was replaced by the intermediate B, and steps (3)-(4) were repeated to obtain the intermediate D3; and so on, steps (3)-(4) were repeated until the intermediate D4 was obtained and the weight gain rate of the intermediate D4 compared with the intermediate D3 was less than 1.5%;

[0034] (6) Cu removal of the intermediate D4: the intermediate D4 was heat treated at 1500 ℃ for 3 h to obtain a porous intermediate E;

[0035] (7) The precursor C was impregnated into the porous intermediate E, and pyrolysis was carried out at 900 ℃ for 3 h to obtain a carbon fiber-ultra-high temperature ceramic composite material.

[0036] Example 2

[0037] A preparation method of a carbon fiber-ultra-high temperature ceramic composite material, the preparation steps are as follows:

[0038] (1), 1# resin, copper powder (particle size 1 μm) are mixed uniformly according to mass ratio 1:0.01, and 1# diluent is added to adjust the slurry viscosity, until the viscosity measured by the cup method is 100 mL slurry flow time 20 s, to obtain precursor A; wherein, 1# resin is liquid furan resin, 1# diluent is dioctyl phthalate;

[0039] (2), precursor A is impregnated into the carbon fiber preform with a density of 0.5 g / cm 3

[0040] (3), 2# resin and ultra-high temperature ceramic particles (particle size 50 nm) are mixed uniformly according to mass ratio 1:0.01, and 2# diluent is added to adjust the slurry viscosity, until the viscosity measured by the cup method is 100 mL slurry flow time 25 s, to obtain precursor C; wherein, 2# resin is liquid furan resin; 1# diluent is dioctyl phthalate; ultra-high temperature ceramic particles are HfC;

[0041] (4), precursor C is first impregnated into intermediate B by PIP method, then cured at 150 ℃ for 2 h, and finally pyrolyzed at 900 ℃ under vacuum for 1 h to obtain intermediate D1;

[0042] (5), intermediate D1 replaces intermediate B, and steps (3)-(4) are repeated to obtain intermediate D2; intermediate D2 replaces intermediate B, and steps (3)-(4) are repeated to obtain intermediate D3; and so on, steps (3)-(4) are repeated until intermediate D5 is obtained and the weight gain rate of intermediate D5 compared with intermediate D4 is less than 1.5%;

[0043] (6), Cu removal of intermediate D5: intermediate D5 is heat treated at 1200 ℃ for 2 h to obtain porous intermediate E;

[0044] (7), precursor C is impregnated into porous intermediate E, and pyrolyzed at 900 ℃ for 2 h to obtain carbon fiber-ultra-high temperature ceramic composite material.

[0045] Example 3

[0046] A preparation method of a carbon fiber-ultra-high temperature ceramic composite material, the preparation steps are as follows:

[0047] (1), 1# resin, copper powder (particle size 5 μm) are mixed uniformly according to mass ratio 1:0.5, and 1# diluent is added to adjust the slurry viscosity, until the viscosity measured by the cup method is 100 mL slurry flow time 70 s, to obtain precursor A; wherein, 1# resin is liquid benzoxazine resin, 1# diluent is toluene;​

[0048] (2) The precursor A is impregnated into a carbon fiber preform with a density of 0.8 g / cm 3 , and pyrolysis is performed at 1100 ℃ under vacuum for 3 h to obtain an intermediate B;

[0049] (3) The 2# resin is uniformly mixed with the ultra-high-temperature ceramic particles (particle size 500 nm) at a mass ratio of 1:0.2, and the 2# diluent is added to adjust the viscosity of the slurry until the viscosity measured by the C-type cup method is 100 mL slurry flow time of 25 s to obtain the precursor C; wherein the 2# resin is a liquid benzoxazine resin; the 1# diluent is toluene; the ultra-high-temperature ceramic particles are ZrC, TaC and HfC mixed in equal mass ratio;

[0050] (4) The precursor C is first impregnated into the intermediate B by PIP method, then cured at 200 ℃ for 5 h, and finally pyrolysis is performed at 1000 ℃ under vacuum for 3 h to obtain an intermediate D1;

[0051] (5) The intermediate D1 is replaced by the intermediate B to repeat steps (3)-(4) to obtain an intermediate D2; the intermediate D2 is replaced by the intermediate B to repeat steps (3)-(4) to obtain an intermediate D3; and so on, repeat steps (3)-(4) until an intermediate D5 is obtained and the weight gain rate of the intermediate D5 compared with the intermediate D4 is less than 1.5%;

[0052] (6) Removing Cu from the intermediate D5: heat treating the intermediate D5 at 1800 ℃ for 4 h to obtain a porous intermediate E;

[0053] (7) Impregnating the precursor C into the porous intermediate E, and pyrolysis at 1000 ℃ for 4 h to obtain a carbon fiber-ultra-high-temperature ceramic composite material.

[0054] Comparative Example 1

[0055] The difference from Example 1 is that no copper powder is added in step (1); correspondingly, there is no step (6) and step (7), and the other steps are the same as those in Example 1; the intermediate D4 obtained in step (5) is the product.

[0056] Performance Test

[0057] The composite materials prepared in Examples 1-3 and Comparative Example 1 are subjected to wind tunnel ablation test and tensile test:

[0058] 1. Wind tunnel ablation test:

[0059] ① The composite material is subjected to 2700 ℃ ablation test in an arc wind tunnel;

[0060] ② Use computer to analyze and monitor the surface topography data of the sample, and record the local small range collapse time of the sample.

[0061] 2. Tensile test: according to GBT 33501-2017 "Carbon / carbon composite tensile test method".

[0062] The results are shown in Table 1. Examples 1-3 use copper powder to form pores, and Comparative Example 1 does not use copper powder. From the test results in Table 1, it can be seen that whether it is a tensile test or a wind tunnel ablation test, Examples 1-3 are better than Comparative Example 1. It shows that the composite material prepared in Examples 1-3 contains more ultra-high temperature ceramic particles.

[0063]

Claims

1. A method for producing a carbon fiber- ultra high temperature ceramic composite material, characterized by, The preparation steps are as follows: (1) 1# liquid resin, copper powder are mixed uniformly according to a mass ratio of 1:(0.01-0.5), and 1# diluent is added to adjust the viscosity of the slurry until the viscosity is 100 mL slurry outflow time of 20-70 s measured by a Zahn cup method, to obtain a precursor A; (2) The precursor A is impregnated into a carbon fiber preform, and pyrolysis is carried out at 900-1100 ℃ under vacuum for 1-3 h to obtain an intermediate B; (3) 2# liquid resin and ultra-high-temperature ceramic particles are mixed uniformly according to a mass ratio of 1:(0.01-0.5), and 2# diluent is added to adjust the viscosity of the slurry until the viscosity is 100 mL slurry outflow time of 20-70 s measured by a Zahn cup method, to obtain a precursor C; (4) The precursor C is impregnated into the intermediate B by a PIP method, and then cured at 150-200 ℃ for 2-5 h, and finally pyrolysis is carried out at 900-1000 ℃ under vacuum for 1-3 h to obtain an intermediate D1; (5), intermediate D2 is obtained by repeating steps (3) - (4) with intermediate D1 instead of intermediate B; intermediate D3 is obtained by repeating steps (3) - (4) with intermediate D2 instead of intermediate B; and so on, until intermediate Dn is obtained by repeating steps (3) - (4) with intermediate Dn-1 instead of intermediate B; n , n > 3 and intermediate Dn n has a weight gain rate of less than 2 % compared to intermediate Dn-1 n-1 ; (6) For intermediate D n Except for Cu: at 1200~1800 ℃, for intermediate D n Heat treatment for 2-4 hours yields porous intermediate E; (7) The precursor C is impregnated into the porous intermediate E, and pyrolysis is carried out at 900-1000 ℃ for 2-4 h to obtain a carbon fiber-ultra-high-temperature ceramic composite material.

2. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that: The particle size of the copper powder is 1-5 μm.

3. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that: The density of the carbon fiber prepreg is 0.5~0.8 g / cm 3 .

4. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that: The particle size of the ultra-high-temperature ceramic particles is 50-1000 nm.

5. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that: The ultra-high-temperature ceramic particles are one or a mixture of several of ZrC, TaC and HfC.

6. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that: The 1# liquid resin and the 2# liquid resin are the same and are selected from one or a mixture of several of phenolic resin, benzoxazine resin, furan resin, polyurea and phenolic modified epoxy resin.

7. The method of claim 6, wherein the carbon fiber- ultra-high-temperature ceramic composite is prepared by the steps of: mixing the carbon fibers and the ceramic precursor; and sintering the mixture to form the carbon fiber- ultra-high-temperature ceramic composite. The furan resin is furfuryl alcohol resin.

8. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that: The 1# diluent and the 2# diluent are the same and are selected from one or a mixture of several of ethanol, toluene, dioctyl phthalate, dibutyl phthalate and triethyl phosphate.

9. The method for preparing carbon fiber-ultra-high temperature ceramic composite material as described in claim 1, characterized in that, In steps (1) and (3), the mass ratio of the 1# liquid resin to the copper powder is 1:(0.05-0.2), and the mass ratio of the 2# liquid resin to the ultra-high-temperature ceramic particles is 1:(0.05-0.2), and the viscosity is 100 mL slurry outflow time of 30-50 s measured by a Zahn cup method.

10. A carbon fiber-ultra-high-temperature ceramic composite material prepared by the preparation method of any one of claims 1-9.

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