CN108129156A - A kind of carbon ceramic composite material and its precursor impregnation preparation method - Google Patents

A kind of carbon ceramic composite material and its precursor impregnation preparation method Download PDF

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CN108129156A
CN108129156A CN201711395103.2A CN201711395103A CN108129156A CN 108129156 A CN108129156 A CN 108129156A CN 201711395103 A CN201711395103 A CN 201711395103A CN 108129156 A CN108129156 A CN 108129156A
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composite material
ceramic composite
carbon
carbon ceramic
precursor
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罗威
江汛
张鸿翔
艾涛
马洋洋
延成宇
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Xi'an Tianyun New Mstar Technology Ltd
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Xi'an Tianyun New Mstar Technology Ltd
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    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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Abstract

The invention discloses a kind of carbon ceramic composite material and its precursor impregnation preparation methods, belong to the preparing technical field of carbon ceramic composite material.The fiber preform of certain density is placed in cvd furnace by the present invention, nitrogen buffer gas, carries out chemical vapor infiltration, high-temperature process is then carried out under nitrogen protection atmosphere；Then the precast body by chemical gaseous phase density is placed in mixture, is taken out and is stood after ultrasonic vibration, then continues in atmosphere furnace and be sintered, and obtains sintering precast body；Finally sintering precast body carries out multiple precursor infiltration and pyrolysis process up to carbon ceramic composite material again.This method is easy to operate, low for equipment requirements, can realize the multi-level density to porous preform.

Description

A kind of carbon ceramic composite material and its precursor impregnation preparation method
Technical field
The invention belongs to the preparing technical fields of carbon ceramic composite material, and in particular to a kind of carbon ceramic composite material and its pioneer Body impregnation preparation method.
Background technology
Carbon ceramic composite material has high intensity, resistance to oxidation, conduction, corrosion-resistant, anti-thermal shock and is easy to a systems such as mechanical processing Row advantage can generate heat in fields such as aerospace, metallurgical industry, mechanical industries as mechanical seal, bearing, mold and high temperature resistant Body has broad application prospects.
Precursor infusion process is currently used for preparing one of main technique of carbon ceramic composite material, using polymeric preceramic Body is impregnated into porous fiber establishment body, and in-situ preparation silicon carbide substrate can be realized by crosslinking curing and Pintsch process, But since cracking small molecule escapes the contraction after forming hole and matrix cracking, the carbon pottery that conventional precursor infusion process is caused to prepare There are 20%~30% inherent porosity, the strong influence overall performances of composite material for composite material.Chemical vapor infiltration Method is to prepare the state-of-the-art technology of fiber reinforced ceramic matric composite, has preparation temperature low (not damaging fiber), can carry out Microstructure and composition design and the advantages of arbitrary shape complex component can be prepared.In chemical gaseous phase permeation process, fiber is pre- Body processed can realize internal filling, so as to fulfill material density.Slurry impregnation and precursor infusion process are combined on this basis, Can be by multilayer secondary design by carbon ceramic composite material density to perfect condition, reduction carbon ceramic composite material porosity improves most The comprehensive performance of whole product.
Application No. is a kind of 201510956421.6 Chinese patents " preparation method and applications of carbon ceramic composite material " Carbon ceramic friction material is prepared for, and be applied to friction material field using chemical vapor deposition and precursor infusion process, shown Good tribological property is shown, but the use of polymethyl silicane has been precursor in the method, density process uses poly- methyl first Silane and styrene mixed liquor are maceration extract, and a large amount of escaping gas are certainly existed in sintering process, matrix is caused to have Compared with concrete dynamic modulus；Chinese patent application No. is 201611084538.0 is with polysilane, dibenzoyl peroxide and silane coupling agent Siliceous precursor solution is mixed to form, carbon ceramic moving part is prepared for by precursor infiltration and pyrolysis technique, is had more smoothly Braking effect.But the siliceous precursor solution used in the method is maceration extract, and thickening technology process relies primarily on infiltration pyrolysis On the one hand process, this more single technique can make material internal generate hole of largely holding one's breath, on the other hand can also increase material table The trepanning number in face influences the final performance of composite material.
Invention content
In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a kind of carbon ceramic composite material and its elder generations Body impregnation preparation method is driven, this method is easy to operate, low for equipment requirements, can realize the multi-level increasing to porous preform It is close, the excellent low porosity carbon ceramic composite material of processability.
The present invention is to be achieved through the following technical solutions：
The invention discloses a kind of precursor impregnation preparation methods of carbon ceramic composite material, include the following steps：
Step 1：It is 0.1~0.49g/cm by density3Fiber preform be placed in cvd furnace, nitrogen buffer gas, into Row chemical vapor infiltration, until the density of fiber preform increases to 1.0~1.1g/cm3, then under nitrogen protection atmosphere, With 2000-2200 DEG C of 2~3h of processing, precast body I is obtained；
Step 2：Precast body I is placed in the mixed slurry of nano carborundum powder and liquid precursor, ultrasonic vibration processing After 2~5h, 2~4h is stood, is then transferred in atmosphere furnace, after being warming up to 1000~1200 DEG C with the heating rate of 2~3 DEG C/min 2~4h is sintered, repeats ultrasonic vibration, standing and sintering operation, until prefabricated volume density increases to 1.8~1.9g/cm3, obtain Precast body II；
Step 3：Precast body II is immersed in maceration extract and carries out impregnation, curing operation is carried out after the completion of dipping, then Pintsch process is carried out in a nitrogen atmosphere, and the material after Pintsch process is repeated into dipping and Pintsch process operation until material Density reach 2.0~2.2g/cm3, carbon ceramic composite material is made.
Preferably, in step 1, fiber preform is 3 D weaving body or fibrofelt.
It is further preferred that the 3 D weaving body is silicon carbide fibre knitted body；The fibrofelt is carbon fiber 3D needles Pierce felt or carbon fiber felt.
Preferably, in step 1, when carrying out chemical vapor infiltration, it is 1.0~1.9KPa, pyrolysis temperature to control air pressure in stove It is 1050~1100 DEG C, selects methane, propylene or propane as carbon-source gas, and carbon-source gas and the volume ratio of carrier gas are (1: 3)~(1:7).
Preferably, in step 2, in the mixed slurry, the mass ratio of nano carborundum powder and liquid precursor is (1: 2)~(1:4).
Preferably, maceration extract described in liquid precursor described in step 2 and step 3 is using liquid Polycarbosilane, And the viscosity of liquid Polycarbosilane at normal temperatures is no more than 2800cp, after 1200 DEG C of sintering in product silicon-carbon atom quality Than being (1:1.0)~(1:1.2), ceramic yield is more than 60%, and ceramic yield refers to remaining solid-state after Polycarbosilane sintering herein Product, including the silicon carbide and trace carbon generated after sintering.
Preferably, in step 3, the impregnation concrete operations are：Vacuum impregnation is first carried out, control vacuum degree is less than 1 ×10-3MPa, dip time are 1~1.5h, are then forced into 0.5~1MPa, 1~1.5h of pressure impregnation.
Preferably, in step 3, curing operation is that the precast body after the completion of dipping is placed in vacuum drying oven, sets vacuum Degree is less than 1 × 10-3MPa, first 0.5~1h of isothermal holding at 120~150 DEG C, then raises temperature to 190~200 DEG C of isothermal holdings 2 ~3h.
Preferably, in step 3, Pintsch process is under protective atmosphere, from room temperature, with the heating speed of 1~2 DEG C/min Rate be warming up to 150~190 DEG C heat preservation 1~2h, then with the heating rate of 0.5~1 DEG C/min be warming up to 500~550 DEG C heat preservation 3~ Then 5h is warming up to 1000~1200 DEG C of 2~3h of heat preservation, finally with the liter of 1~2 DEG C/min with the heating rate of 2~3 DEG C/min Warm rate is warming up to 1650~1900 DEG C of 5~8h of heat preservation.
The invention also discloses using carbon ceramic composite material made from above-mentioned precursor impregnation preparation method, which makes pottery compound The porosity of material is 6%~9%.
Compared with prior art, the present invention has technique effect beneficial below：
The precursor impregnation preparation method of carbon ceramic composite material disclosed by the invention is designed, passing through using multilayer density It learns gas-phase permeation technology and realizes density inside fiber preform, avoid lacking more than hole of holding one's breath inside existing precursor impregnation technology It falls into；Meanwhile with unique ultrasonic immersing technique, by nanometer silicon carbide powder filling precast body middle level, and pass through subsequent high temperature and consolidate Phase sintering realizes integrated ceramic；A small amount of spalttupfel of first two steps technique generation is finally filled up by precursor impregnation technology again Gap realizes prefabricated volume surrounding densification, finally prepares the low porosity carbon ceramic composite material haveing excellent performance.This method operation letter It is single, it is low for equipment requirements, it can realize the multi-level density to porous preform.
Porosity not more than 10% through carbon ceramic composite material produced by the present invention, it is far superior to of the prior art Carbon ceramic composite material is had excellent performance there are 20%~30% inherent porosity.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
Embodiment 1
A kind of precursor impregnation preparation method of carbon ceramic composite material, includes the following steps：
Step 1：It is 0.15g/cm by density3Carbon fiber felt be placed in cvd furnace, nitrogen buffer gas, methane is carbon Source gas body carries out chemical vapor infiltration, until fibre preforms volume density increases to 1.1g/cm3, then protected in 2100 DEG C of nitrogen High-temperature process 2.5h under atmosphere, obtains precast body I, and wherein chemical vapor infiltration concrete technology is：Carbon-source gas and carrier gas volume Than being 1:7, control air pressure 1.9KPa in cvd furnace, 1100 DEG C of pyrolysis temperature；
Step 2：Precast body I is placed in mixture, ultrasonic vibration 2h, then takes out and stand 2h, be transferred in atmosphere furnace with The heating rate of 3 DEG C/min is warming up to 1100 DEG C of sintering 3h, ultrasonic vibration-standing-sintering process is repeated, until prefabricated volume density Reach 1.80g/cm3, obtain precast body II, wherein the specific proportioning of mixture for nano carborundum powder and liquid precursor according to Mass ratio 1:3；
Step 3：Precast body II is immersed in maceration extract, carries out 1.5h vacuum impregnations first, control vacuum degree is not more than 1 ×10-3MPa, then the pressure impregnation 1.3h under 0.7MPa, dipping are transferred to baking oven setting vacuum degree and are not more than 1 × 10 after the completion- 3MPa, keeps the temperature 1h at 130 DEG C, is continuously heating to 190 DEG C of heat preservation 3h after the completion, then takes out the precast body that will be cured in nitrogen Pintsch process is carried out under gas atmosphere, specific cracking technology is to be warming up to 150 DEG C of heat preservation 2h, then be warming up to 1 DEG C/min with 0.5 DEG C Then 550 DEG C of heat preservation 5h are warming up to 1000 DEG C of heat preservation 3h with 3 DEG C/min, be finally warming up to 1900 DEG C of heat preservation 8h with 1 DEG C/min, Last repeated impregnations-cracking process is until density of material reaches 2.0g/cm3To get carbon ceramic composite material.
Embodiment 2
A kind of precursor impregnation preparation method of carbon ceramic composite material, includes the following steps：
Step 1：It is 0.40g/cm by density3Carbon fiber 3D Nomexs be placed in cvd furnace, nitrogen buffer gas, first Alkane carries out chemical vapor infiltration for carbon-source gas, until fibre preforms volume density increases to 1.0g/cm3, then in 2000 DEG C of nitrogen High-temperature process 2h under gas shielded atmosphere, obtains precast body I, and wherein chemical vapor infiltration concrete technology is：Carbon-source gas and carrier gas Volume ratio is 1:4, control air pressure 1.4KPa in cvd furnace, 1050 DEG C of pyrolysis temperature；
Step 2：Precast body I is placed in mixture, ultrasonic vibration 3h, then takes out and stand 4h, be transferred in atmosphere furnace with The heating rate of 2 DEG C/min is warming up to 1000 DEG C of sintering 4h, ultrasonic vibration-standing-sintering process is repeated, until prefabricated volume density Reach 1.85g/cm3, obtain precast body II, wherein the specific proportioning of mixture for nano carborundum powder and liquid precursor according to Mass ratio 1:2；
Step 3：Precast body II is immersed in maceration extract, carries out 1h vacuum impregnations first, control vacuum degree no more than 1 × 10-3MPa, then the pressure impregnation 1h under 0.5MPa, dipping are transferred to baking oven setting vacuum degree and are not more than 1 × 10 after the completion-3MPa, 0.5h is kept the temperature at 150 DEG C, is continuously heating to 200 DEG C of heat preservation 2h after the completion, then takes out the precast body that will be cured in nitrogen gas Pintsch process is carried out under atmosphere, specific cracking technology is to be warming up to 180 DEG C of heat preservation 1h, then be warming up to 500 DEG C with 1 DEG C with 2 DEG C/min 3h is kept the temperature, 1100 DEG C of heat preservation 2h are then warming up to 2 DEG C/min, 1700 DEG C of heat preservation 5h are finally warming up to 2 DEG C/min, are finally weighed Multiple dipping-cracking process is until density of material reaches 2.0g/cm3To get carbon ceramic composite material.
Embodiment 3
A kind of precursor impregnation preparation method of carbon ceramic composite material, includes the following steps：
Step 1：It is 0.49g/cm by density3Silicon carbide fibre knitted body be placed in cvd furnace, nitrogen buffer gas, Methane carries out chemical vapor infiltration for carbon-source gas, until fibre preforms volume density increases to 1.05g/cm3, then at 2200 DEG C High-temperature process 3h under nitrogen protection atmosphere, obtains precast body I, and wherein chemical vapor infiltration concrete technology is：Carbon-source gas is with carrying Air volume ratio is 1:3, control air pressure 1.0KPa in cvd furnace, 1080 DEG C of pyrolysis temperature；
Step 2：Precast body I is placed in mixture, ultrasonic vibration 5h, then takes out and stand 3h, be transferred in atmosphere furnace with The heating rate of 3 DEG C/min is warming up to 1200 DEG C of sintering 2h, ultrasonic vibration-standing-sintering process is repeated, until prefabricated volume density Reach 1.9g/cm3, obtain precast body II, wherein the specific proportioning of mixture for nano carborundum powder and liquid precursor according to Mass ratio 1:4；
Step 3：Precast body II is immersed in maceration extract, carries out 1.5h vacuum impregnations first, control vacuum degree is not more than 1 ×10-3MPa, then the pressure impregnation 1.5h under 1MPa, dipping are transferred to baking oven setting vacuum degree and are not more than 1 × 10 after the completion-3MPa, 1h is kept the temperature at 130 DEG C, is continuously heating to 200 DEG C of heat preservation 3h after the completion, then takes out the precast body that will be cured in nitrogen gas Pintsch process is carried out under atmosphere, specific cracking technology is to be warming up to 160 DEG C of heat preservation 1.5h, then be warming up to 1 DEG C/min with 0.5 DEG C Then 550 DEG C of heat preservation 5h are warming up to 1000 DEG C of heat preservation 3h with 2.5 DEG C/min, are finally warming up to 1650 DEG C of heat preservations with 1 DEG C/min 8h, last repeated impregnations-cracking process is until density of material reaches 2.2g/cm3To get carbon ceramic composite material.
Embodiment 4
A kind of precursor impregnation preparation method of carbon ceramic composite material, includes the following steps：
Step 1：It is 0.1g/cm by density3Silicon carbide fibre knitted body be placed in cvd furnace, nitrogen buffer gas, first Alkane carries out chemical vapor infiltration for carbon-source gas, until fibre preforms volume density increases to 1.0g/cm3, then in 2100 DEG C of nitrogen High-temperature process 3h under gas shielded atmosphere, obtains precast body I, and wherein chemical vapor infiltration concrete technology is：Carbon-source gas and carrier gas Volume ratio is 1:3, control air pressure 1.0KPa in cvd furnace, 1080 DEG C of pyrolysis temperature；
Step 2：Precast body I is placed in mixture, ultrasonic vibration 5h, then takes out and stand 3h, be transferred in atmosphere furnace with The heating rate of 3 DEG C/min is warming up to 1200 DEG C of sintering 2h, ultrasonic vibration-standing-sintering process is repeated, until prefabricated volume density Reach 1.9g/cm3, obtain precast body II, wherein the specific proportioning of mixture for nano carborundum powder and liquid precursor according to Mass ratio 1:3；
Step 3：Precast body II is immersed in maceration extract, carries out 1.5h vacuum impregnations first, control vacuum degree is not more than 1 ×10-3MPa, then the pressure impregnation 1.5h under 1MPa, dipping are transferred to baking oven setting vacuum degree and are not more than 1 × 10 after the completion-3MPa, 1h is kept the temperature at 120 DEG C, is continuously heating to 200 DEG C of heat preservation 3h after the completion, then takes out the precast body that will be cured in nitrogen gas Pintsch process is carried out under atmosphere, specific cracking technology is to be warming up to 190 DEG C of heat preservation 2h, then be warming up to 550 with 0.5 DEG C with 1 DEG C/min DEG C heat preservation 5h, then with 2.5 DEG C/min be warming up to 1200 DEG C heat preservation 3h, finally with 1 DEG C/min be warming up to 1750 DEG C heat preservation 6h, most Repeated impregnations-cracking process is until density of material reaches 2.1g/cm afterwards3To get carbon ceramic composite material.
The present invention carries out porosity measurement to carbon ceramic composite material prepared by Examples 1 to 4, and the results are shown in Table 1.
1 porosity measurement result of table
Porosity
Embodiment 1 6%
Embodiment 2 9%
Embodiment 3 8%
Embodiment 4 7%
As can be seen that the porosity of carbon ceramic composite material not more than 10% being prepared through the method for the present invention, far Being much better than carbon ceramic composite material of the prior art, there are 20%~30% inherent porosities.The present invention is by the fiber of certain density Precast body is placed in cvd furnace, nitrogen buffer gas, carries out chemical vapor infiltration, high temperature is then carried out under nitrogen protection atmosphere Processing；Then the precast body by chemical gaseous phase density is placed in mixture, is taken out and is stood after ultrasonic vibration, then continues at gas It is sintered in atmosphere stove, obtains sintering precast body；Finally sintering precast body carries out multiple precursor infiltration and pyrolysis process again to obtain the final product Carbon ceramic composite material.The present invention is designed using multilayer density, using chemical vapor infiltration technology as support, inside density precast body, Reduce the generation in hole of holding one's breath；With unique ultrasonic immersing technique, by nanometer silicon carbide powder filling precast body middle level, and pass through height Warm solid-phase sintering realizes integrated ceramic；Finally fill up a small amount of of first two steps technique generation by precursor impregnation technology again and split Pit gap realizes prefabricated volume surrounding densification, finally prepares the low porosity carbon ceramic composite material haveing excellent performance.

Claims (10)

1. a kind of precursor impregnation preparation method of carbon ceramic composite material, which is characterized in that include the following steps：
Step 1：It is 0.1~0.49g/cm by density3Fiber preform be placed in cvd furnace, nitrogen buffer gas is changed Gas-phase permeation is learned, until the density of fiber preform increases to 1.0~1.1g/cm3, then under nitrogen protection atmosphere, with 2000-2200 DEG C of 2~3h of processing, obtains precast body I；
Step 2：Precast body I is placed in the mixed slurry of nano carborundum powder and liquid precursor, ultrasonic vibration processing 2~ After 5h, 2~4h is stood, is then transferred in atmosphere furnace, is burnt after being warming up to 1000~1200 DEG C with the heating rate of 2~3 DEG C/min 2~4h of knot repeats ultrasonic vibration, standing and sintering operation, until prefabricated volume density increases to 1.8~1.9g/cm3, obtain pre- Body II processed；
Step 3：Precast body II is immersed in maceration extract and carries out impregnation, curing operation is carried out after the completion of dipping, then in nitrogen Pintsch process is carried out under gas atmosphere, by the material after Pintsch process repeat dipping and Pintsch process operation until material it is close Degree reaches 2.0~2.2g/cm3, carbon ceramic composite material is made.
2. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that step 1 In, fiber preform is 3 D weaving body or fibrofelt.
3. the precursor impregnation preparation method of carbon ceramic composite material according to claim 2, which is characterized in that the three-dimensional Knitted body is silicon carbide fibre knitted body；The fibrofelt is carbon fiber 3D Nomexs or carbon fiber felt.
4. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that step 1 In, when carrying out chemical vapor infiltration, air pressure is 1.0~1.9KPa in control stove, pyrolysis temperature is 1050~1100 DEG C, selects first Alkane, propylene or propane are as carbon-source gas, and carbon-source gas and the volume ratio of carrier gas are (1:3)~(1:7).
5. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that step 2 In, in the mixed slurry, the mass ratio of nano carborundum powder and liquid precursor is (1:2)~(1:4).
6. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that in step 2 Maceration extract described in the liquid precursor and step 3 is using liquid Polycarbosilane, and the liquid Polycarbosilane is at normal temperatures Viscosity be no more than 2800cp, the mass ratio of silicon-carbon atom is (1 in product after 1200 DEG C of sintering:1.0)~(1:1.2) it, burns The ceramic yield for tying product is more than 60%.
7. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that step 3 In, the impregnation concrete operations are：Vacuum impregnation is first carried out, control vacuum degree is less than 1 × 10-3MPa, dip time 1 Then~1.5h is forced into 0.5~1MPa, 1~1.5h of pressure impregnation.
8. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that step 3 In, curing operation is that the precast body after the completion of dipping is placed in vacuum drying oven, and setting vacuum degree is less than 1 × 10-3MPa first exists 0.5~1h of isothermal holding at 120~150 DEG C then raises temperature to 190~200 DEG C of 2~3h of isothermal holding.
9. the precursor impregnation preparation method of carbon ceramic composite material according to claim 1, which is characterized in that step 3 In, Pintsch process is under protective atmosphere, and from room temperature, 150~190 DEG C of heat preservations are warming up to the heating rate of 1~2 DEG C/min 1~2h, then 500~550 DEG C of 3~5h of heat preservation are warming up to the heating rate of 0.5~1 DEG C/min, then with 2~3 DEG C/min's Heating rate is warming up to 1000~1200 DEG C of 2~3h of heat preservation, finally 1650 are warming up to the heating rate of 1~2 DEG C/min~ 1900 DEG C of 5~8h of heat preservation.
10. using carbon ceramic composite material made from the precursor impregnation preparation method described in any one in claim 1~9, It is characterized in that, the porosity of the carbon ceramic composite material is 6%~9%.
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CN109180194A (en) * 2018-09-28 2019-01-11 中国人民解放军第五七九工厂 A kind of compound density method of the different conditions polymer infiltration and pyrolysis of SiC based composites
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CN110563478A (en) * 2019-10-15 2019-12-13 航天特种材料及工艺技术研究所 fiber-reinforced ceramic matrix composite material and preparation method and application thereof
CN110563478B (en) * 2019-10-15 2022-02-01 航天特种材料及工艺技术研究所 Fiber-reinforced ceramic matrix composite material and preparation method and application thereof

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