CN106565262A - Preparation method for low-density refractory and antioxidative carbon-ceramic composite material - Google Patents
Preparation method for low-density refractory and antioxidative carbon-ceramic composite material Download PDFInfo
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Abstract
The invention relates to a preparation method for a low-density refractory and antioxidative carbon-ceramic composite material. The low-density carbon-ceramic composite material is formed through compounding a lightweight carbon fibre heat-isolation body with a high porosity with refractory and antioxidative ceramic. The preparation method is characterized in that a ceramic phase is controllably and uniformly introduced into the surfaces of carbon fibres and the pores of the heat-isolation body. The mechanical strength of the carbon fibre heat-isolation body with the high porosity can be obviously increased, and the antioxidative capacity thereof can be obviously improved due to the introduction of the ceramic phase, and the characteristic of low thermal conductivity is achieved. The low-density refractory and antioxidative carbon-ceramic composite material prepared by the preparation method disclosed by the invention has a great application value in the fields of advanced thermal protection materials and advanced heat-isolation materials under a high-temperature aerobic environment.
Description
Technical field
The preparation method of heat-insulation composite material the present invention relates to a kind of low-density infusibility oxidation resistant carbon is made pottery, is mainly used in non-burning
Erosion thermal protection system field, belongs to the preparing technical field of carbon ceramic composite material.
Background technology
When aircraft is with Hypersonic reentry atmosphere, the Aerodynamic Heating of the key position such as sharp nose cone, nose of wing
Temperature is up to 2000 DEG C, has high requirement to thermal protection system material.For Reusable launch vehicles, nose cone, the wing
The key positions such as leading edge in Hypersonic reentry atmosphere, by Strong shear, 2000 DEG C or so of high temperature and aerobic environment
Test, it is desirable to which material has thermal structure stability, effective solar heat protection and heat-insulated, antioxidant anticorrosive, non-ablative or micro-ablation, resists
The harsh performances such as airflow scouring shearing.
U.S. space shuttle thermal protection system adopts non-ablative ceramic insulation watt as heat insulation material, can be at 1200 DEG C
Use when long in aerobic environment.Ceramic insulation watt in space shuttle is main with quartz fibre as raw material, makes through 3D bondings
Low-density high porosity ceramic thermal insulation tile, coat special oxidation-resistant ceramic coating on surface, common ripe ceramic tile has
AETB, AIM, FRCI, TUFI of the LI-900 of Lockheed Co.'s exploitation, NASA exploitation etc..(US Patent 5079082, US
Patent 4148962, US Patent 5629186, US Patent 6030698).
Because traditional anti-heat-barrier material of ceramic insulation watt non-ablative is mainly formed by chopped quartz fibre bonding, therefore make
It is limited with temperature, typically use safely below 1300 DEG C, and ceramic tile material fragility itself is big, and thermal shock resistance is poor.It is superb
The thermally protective materials of the key positions such as the repeatable aerospace craft nose cone of the velocity of sound, nose of wing must are fulfilled for high temperature (1600 DEG C of ＞) chi
The stability of very little and structure, the non-oxidizability having under oxidation environment, efficient non-ablative solar heat protection and heat-insulated.Carbon-based heat-barrier material is lazy
Property atmosphere under there is splendid Temperature Size and structural stability, lower thermal conductivity and the characteristics of high porosity, energy under inert atmosphere
It is enough in more than 2000 DEG C of hot environment.But, carbon-based heat-barrier material non-oxidizability is poor in high temperature aerobic environment, it is impossible to single
It is private to make heat-barrier material.
The content of the invention
The present invention technology solve problem be：Overcome the deficiencies in the prior art, propose a kind of low-density infusibility oxidation resistant carbon
The preparation method of ceramic composite material, the method is not enough for porous heat-barrier material high-temperature oxidation resistance, using polymer
The method of presoma dipping-cracking, on porous carbon base carbon fibre surface oxidation-resistant ceramic phase is introduced, and improves carbon-based heat-barrier material
High-temperature oxidation resistance, mechanical strength and thermal structure stability.Overcome the carbon-based heat-barrier material non-oxidizability of high porosity and machine
Tool intensity is not enough, and the method is prepared for the low-density infusibility oxidation resistant carbon ceramic composite material with high temperature resistant, antioxidant characteristics.
The present invention technical solution be：
The step of a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material, the method, includes：
(1) the Polymer ceramic precursor solution that mass concentration is 5%～60% is prepared, is stirred, be prepared into dipping
Liquid；
(2) high porosity carbon fiber matter heat-barrier material is put in closed mold, vacuumizes 30～60min, then will step
Suddenly the maceration extract for preparing in (1) is transferred at room temperature in closed mold, 60～120min of vacuum impregnation, after dipping
Carbon fiber matter heat-barrier material takes out from closed mold, and 2～12h is dried under the conditions of -60 DEG C of air at room temperature；
(3) it is the dried carbon fiber matter heat-barrier material of step (2) is fast with the intensification of 3～10 DEG C/min under inert atmosphere
Rate is warming up to 170～220 DEG C, solidification 60～180min of crosslinking, then proceed to the ramp of 2～5 DEG C/min to 900～
1400 DEG C, 60～120min of Pintsch process, cracking is down to room temperature after finishing with the speed of 3～10 DEG C/min；
(4) according to sample density, intensity and ceramic phase content requirement, repeat step (2) and (3) are multiple, such as 2-10 time,
Obtain low-density infusibility oxidation resistant carbon ceramic composite material.
In described step (1), Polymer ceramic precursor includes poly- silicon-carbon alkane, polysilazane, the poly- silicon-carbon containing B element
One kind in alkane, polysiloxanes；
In described step (1), before the solvent adopted during prepared polymer ceramics precursor liquid solution is for polymer-ceramic
Drive the good solvent of body, the such as one kind in dimethylbenzene, toluene, benzene, n-hexane, ethanol, tetrahydrofuran, chloroform；
In described step (2), high porosity carbon fiber matter heat-barrier material be chopped carbon fiber acupuncture rigidly heat-insulated carbon felt,
The flexible heat-insulated carbon felt of chopped carbon fiber acupuncture, the heat-insulated carbon felt of rigidity of chopped carbon fiber braiding, chopped carbon fiber braiding and
Into flexible heat-insulated carbon felt, high porosity 3D rigidity carbon bonding thermal insulation tiles in one kind, high porosity carbon fiber matter heat-barrier material
Density be 0.15～0.50g/cm3, porosity is 70%～95%；
Described low-density infusibility oxidation resistant carbon ceramic composite material, including high porosity cellulosic heat-barrier material skeleton and difficulty
Molten oxidation-resistant ceramic matrix；Ceramic matrix is coated on around carbon fiber, is evenly distributed in porous heat insulation material skeleton, plays guarantor
Shield carbon fiber is oxidized and strengthens the effect of heat-barrier material skeleton.
Ceramic phase component is transformed by Polymer ceramic precursor cracking in described low density carbon ceramic composite material,
Comprising atoms such as Si, C, O, B, N, with high temperature resistant, anti-oxidant, high intensity feature, cracking temperature 900～1400 DEG C it
Between, inert atmosphere.
Mass fraction in described low-density infusibility oxidation resistant carbon ceramic composite material shared by ceramic phase component 30%～
Between 80%, between 70%～20%, density is 0.30～1.20g/cm to the mass fraction of fibre fractionation3。
In order to obtain the low density carbon ceramic composite material of lightweight, porous and some strength, described polymer ceramic precursor
Body dipping-cracking process needs to repeat 2～10 times.
The low-density infusibility oxidation resistant carbon pottery heat-insulation composite material that the present invention is provided has compared with common carbon ceramic composite material
There is following advantage：
(1) preparation process is simple, it is convenient to carry out, it is easy to which that scale is amplified；
(2) with lightweight, porous the characteristics of, disclosure satisfy that the demand of equipment and aircraft lightweighting materials；
(3) by changing the parameters such as Polymer ceramic precursor species, dipping number of times, cracking technology, can prepare suitable
For the diversified low density carbon pottery heat-insulation composite material of different condition；
(4) mechanics of materials intensity increases significantly compared with original carbon felt heat-barrier material, and antioxygenic property is obvious to be obtained
To improvement.
(5) certain density Polymer ceramic precursor maceration extract is prepared, with the heat-insulated material of high porosity carbon felt of commercialization
Material or the heat-insulated carbon watt impregnated polymer maceration extract of high porosity 3D rigidity carbon bondings, then high anneal crack in an inert atmosphere again
Solution, is repeated several times the process, is met the low-density infusibility oxidation resistant carbon ceramic composite material of condition；
(6) the present invention relates to a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material.The low density carbon pottery
Composite is composited by the lightweight carbon fiber matter insulator and infusibility oxidation-resistant ceramic of high porosity, and preparation it is critical only that
Carbon fiber surface and insulator hole are uniformly introduced by ceramic phase is controllable.The introducing of ceramic phase can significantly improve high hole
The mechanical strength and oxidation resistance of gap rate carbon fiber heat insulation body, while the characteristic led with low-heat.Prepared by the present invention low close
Advanced heat-barrier material field tool of the degree infusibility oxidation resistant carbon ceramic composite material under advanced thermally protective materials and high temperature aerobic environment
There is great using value.
Description of the drawings
Fig. 1 is embodiment 1,2,4 and is not impregnated with the aerial thermogravimetric curve of carbon felt；
Fig. 2 is the SEM photograph in the sample of embodiment 1 inside and carbon fiber section；
Fig. 3 is carbon fiber cross section elemental line scan curve and SEM photograph in the sample of embodiment 1；
Fig. 4 is carbon fiber cross section elemental line scan curve and SEM photograph in the sample of embodiment 4；
Fig. 5 is the preparation process schematic diagram of the carbon ceramic composite material of the present invention.
Specific embodiment
A kind of low-density infusibility oxidation resistant carbon ceramic composite material, its composition is comprising high porosity lightweight reinforcement and high temperature resistant
Oxidation-resistant ceramic matrix, low-density, high temperature oxidation resisting.
The reinforcement is 3D carbon bondings chopped carbon fiber rigidity thermal insulation tile, acupuncture carbon fiber heat insulation felt and a series of commodity
Change carbon fiber heat insulation felt body, density is in 0.15～0.50g/cm3Between, porosity is between 70～95%；Described low-density
Infusibility oxidation resistant carbon ceramic composite material, between 30～80%, the mass content of fibre fractionation is 70% for ceramic phase mass content
Between～20%, density is in 0.30～1.20g/cm3Between.
Described low density carbon ceramic composite material is, with low-density high porosity carbon fiber as skeleton structure, to be gathered by dipping
The mode of compound precursor solution-cracking is filled in fiber reinforcement with fiber surface and mutually obtained with coating ceramic.
Described presoma dipping solution concentration is between 5～60%；Described solvent is to common are machine solvent, such as two
Toluene, toluene, benzene, n-hexane, normal heptane, ethanol, tetrahydrofuran etc.；Described Polymer ceramic precursor is before SiC ceramic
Drive the poly- silicon-carbon alkane of body, the poly- borosilicate carbon alkane of SiBCN ceramic forerunners, SixNyCeramic forerunner polysilazane etc..
Low-density infusibility oxidation resistant carbon ceramic composite material, described method at least comprises the steps：
(1) certain density Polymer ceramic precursor dipping solution is prepared；
(2) high porosity cellulosic heat-barrier material is put in closed mold, vacuumizes 30～60min, step is matched somebody with somebody in (1)
The impregnating agent of system is transferred at room temperature in closed mold, 60～120min of vacuum impregnation, is then dried 2～12h；
(3) the cellulosic heat-barrier material after step (2) is impregnated is under inert atmosphere with the heating rate of 2～10 DEG C/min
Elevated cure, cracking, cracking is down to room temperature after finishing with the speed of 3～10 DEG C/min；
(4) according to sample density, intensity and ceramic phase content requirement, repeat step (2) and (3) are repeatedly.
With reference to case is embodied as, the invention will be further elaborated, but the invention is not restricted to following enforcement case
Example, methods described is if no special instructions conventional method, and the material can be obtained if no special instructions from open commercial sources
.
Embodiment 1
The poly- silicon-carbon alkane 68.3780g of SiC ceramic presoma is weighed, in being dissolved in the n-hexane solvent of 389.1g, matter is configured to
The maceration extract of amount fraction 15wt%.By 30 × 30 × 30mm33D carbon bonding rigidity carbon felt insulator 4.0354g be positioned over closing
In mould, after vacuumizing 30min, vacuum is closed, above-mentioned maceration extract is transferred in closed mould, vacuum impregnation 60min.Will leaching
Carbon felt after stain is taken out from closed mold and is dried 3h in 45 DEG C of baking ovens, be then placed in the tube furnace of argon gas atmosphere with
The temperature of 10 DEG C/min rises to 220 DEG C, heat preservation solidification 2h, then rises to 1200 DEG C with the heating rate of 3 DEG C/min, insulation cracking 2h
Afterwards, room temperature is down to the speed of 5 DEG C/min, obtains composite sample quality for 5.2368g.The above-mentioned dipping of repetition-cracked
Cheng Sanci, the quality of the low density carbon pottery heat-insulation composite material for finally giving is 8.0252g, and density is 0.3009g/cm3, ceramics
Yield average out to 73.5%.
Table 1 is the weight-loss ratio of composite sample under the conditions for the treatment of of different temperature, in table 1 under argon gas and air atmosphere
It can be seen that having impregnated the low density carbon ceramic composite material that SiC presomas obtain has certain non-oxidizability.
The compression performance of low density carbon pottery heat-insulation composite material of the table 2 to obtain, testing standard is GB/T1448-2005.
Embodiment 2
The poly- silicon-carbon alkane 68.3780g of SiC ceramic presoma is weighed, in being dissolved in the n-hexane solvent of 389.1g, matter is configured to
The maceration extract of amount fraction 15wt%.By 30 × 30 × 30mm33D carbon bonding rigidity carbon felt insulator 3.7676g be positioned over closing
In mould, after vacuumizing 30min, vacuum is closed, above-mentioned maceration extract is transferred in closed mould, vacuum impregnation 60min.Will leaching
Carbon felt after stain is taken out from closed mold and is dried 3h in 45 DEG C of baking ovens, be then placed in the tube furnace of argon gas atmosphere with
The temperature of 10 DEG C/min rises to 220 DEG C, heat preservation solidification 2h, then rises to 1200 DEG C with the heating rate of 3 DEG C/min, insulation cracking 2h
Afterwards, room temperature is down to the speed of 5 DEG C/min, obtains composite sample quality for 5.1264g.The above-mentioned dipping of repetition-cracked
Cheng Wuci, the quality of the low density carbon pottery heat-insulation composite material for finally giving is 10.9266g, and density is 0.4047g/cm3, put down
Ceramic yield is 74.2%.
Embodiment 3
The poly- silicon-carbon alkane 70.4255g of SiC ceramic presoma is weighed, in being dissolved in the n-hexane solvent of 164.1210g, is prepared
Into the maceration extract of mass fraction 30wt%.By 30 × 30 × 30mm33D carbon bonding rigidity carbon felt insulator 4.1555g be positioned over
In closed mould, after vacuumizing 30min, vacuum is closed, above-mentioned maceration extract is transferred in closed mould, vacuum impregnation 90min.
Carbon felt after dipping is taken out from closed mold and is dried 3h in 45 DEG C of baking ovens, be then placed into the tube furnace of argon gas atmosphere
In rise to 220 DEG C with the temperature of 10 DEG C/min, heat preservation solidification 2h, then 1300 DEG C are risen to the heating rate of 3 DEG C/min, insulation is split
After solution 2h, room temperature is down to the speed of 5 DEG C/min, obtains composite sample quality for 6.3391g.The above-mentioned dipping of repetition-split
Twice, the quality of the low density carbon pottery heat-insulation composite material for finally giving is 9.9063g to solution preocess, and density is 0.3669g/cm3,
Ceramic yield average out to 70.2%.
Embodiment 4
The poly- borosilicate carbon alkane 90.4255g of SiBCN ceramic forerunners is weighed, in being dissolved in the ethyl acetate solvent of 361.70g,
It is configured to the maceration extract of mass fraction 20wt%.By 30 × 30 × 30mm33D carbon bonding rigidity carbon felt insulator 4.3230g put
In being placed in closed mould, after vacuumizing 60min, vacuum is closed, above-mentioned maceration extract is transferred in closed mould, vacuum impregnation
60min.Carbon felt after dipping is taken out from closed mold and is dried 3h in 45 DEG C of baking ovens, be then placed into argon gas atmosphere
220 DEG C are risen to the temperature of 5 DEG C/min in tube furnace, solid 3h is incubated, then 1200 DEG C are risen to the heating rate of 3 DEG C/min, protected
After anneal crack solution 2h, room temperature is down to the speed of 5 DEG C/min, obtains composite sample quality for 5.6300g.The above-mentioned leaching of repetition
Stain-cracking process three times, the quality of the low density carbon pottery heat-insulation composite material for finally giving is 9.1458g, and density is
0.3387g/cm3, ceramic yield average out to 57.6%.
Embodiment 5
The poly- silicon-carbon alkane 1968.5g of SiC ceramic presoma is weighed, in being dissolved in the toluene solvant of 1300.0g, quality is configured to
The maceration extract of fraction 60wt%.By 225 × 140 × 70mm33D carbon bonding rigidity carbon felt insulator 398.3g be positioned over closing
In mould, after vacuumizing 60min, vacuum is closed, above-mentioned maceration extract is transferred in closed mould, vacuum impregnation 180min.Will
Carbon felt after dipping is taken out from closed mold and is dried 3h in 75 DEG C of baking ovens, in being then placed into the high temperature furnace of argon gas atmosphere
220 DEG C are risen to the temperature of 10 DEG C/min, solid 3h is incubated, then 1000 DEG C are risen to the heating rate of 3 DEG C/min, insulation cracking 2h
Afterwards, room temperature is down to the speed of 5 DEG C/min, it is 1433.7g to obtain composite sample quality, and density is 0.65g/cm3, ceramics
Yield is 77.4%.
Embodiment 6
SiOC ceramic forerunner polysiloxanes 100.2011g are weighed, in being dissolved in the ethyl acetate solvent of 15.2884g, is matched somebody with somebody
Make the maceration extract of mass fraction 40wt%.By 20 × 20 × 15mm33D carbon bonding rigidity carbon felt insulator 2.7221g place
In closed mould, after vacuumizing 30min, vacuum is closed, above-mentioned maceration extract is transferred in closed mould, vacuum impregnation
60min.Carbon felt after dipping is taken out from closed mold and is dried 3h in 60 DEG C of baking ovens, be then placed into argon gas atmosphere
220 DEG C are risen to the temperature of 10 DEG C/min in tube furnace, solid 3h is incubated, then 1000 DEG C are risen to the heating rate of 3 DEG C/min, protected
After anneal crack solution 2h, room temperature is down to the speed of 5 DEG C/min, obtains composite sample quality for 3.8852g.The above-mentioned leaching of repetition
Stain-cracking process three times, the quality of the carbon ceramic composite material for finally giving is 4.8746g, and density is 0.3522g/cm3, averagely
Ceramic yield is 68.8%.
Embodiment 7
Weigh SiC ceramic presoma poly- silicon-carbon alkane 960.4g, zirconium-n-butylate 482.2g, be dissolved in 1445.6g just oneself
In alkane solvents, the polysilazane maceration extract containing zirconium-n-butylate of mass fraction 40wt% is configured to.It is 0.18g/cm by density3
Commercialization carbon felt (purchase of Qingdao Bao Tai companies) 224.8g be positioned in closed mould, after vacuumizing 60min, close vacuum,
Above-mentioned maceration extract is transferred in closed mould, vacuum impregnation 60min.By the carbon felt after dipping take out from closed mold after
5h is dried in 50 DEG C of baking ovens, is then placed in the high temperature furnace of argon gas atmosphere rising to 220 DEG C with the temperature of 10 DEG C/min, insulation is solid
Change 3h, then 1000 DEG C are risen to the heating rate of 2 DEG C/min, after insulation cracking 2h, room temperature is down to the speed of 3 DEG C/min, obtain
It is 492.6g to composite sample quality, the quality of the carbon ceramic composite material for finally giving is 4.8746g, and density is 0.39g/
cm3, average ceramic yield is 86.3%.
Embodiment 8
The poly- silicon-carbon alkane 68.3780g of SiC ceramic presoma is weighed, in being dissolved in the n-hexane solvent of 389.1g, matter is configured to
The maceration extract of amount fraction 15wt%.By 137 × 147 × 41mm3Commercialization carbon felt (CALCARB) carbon bonding rigidity carbon felt it is heat-insulated
Body 124.98g is positioned in closed mould, after vacuumizing 60min, closes vacuum, and above-mentioned maceration extract is transferred to into closed mould
In, vacuum impregnation 90min.Carbon felt after dipping is taken out from closed mold and is dried 3h in 45 DEG C of baking ovens, then placed
220 DEG C are risen in tube furnace with the temperature of 10 DEG C/min, heat preservation solidification 2h, then rise to 1200 with the heating rate of 3 DEG C/min
DEG C, after insulation cracking 2h, room temperature is down to the speed of 5 DEG C/min, composite sample quality is obtained for 165.39g.In repetition
Dipping-cracking process three times is stated, the quality of the low density carbon pottery heat-insulation composite material for finally giving is 257.20g, and density is
0.37g/cm3, ceramic yield average out to 80.2%.The sample of 1 embodiment of table 1 is weightless under different temperatures under argon gas and air atmosphere
Rate
The low density carbon ceramic composite material compression performance of table 2
Claims (6)
1. a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material, it is characterised in that include the step of the method：
(1) the Polymer ceramic precursor solution that mass concentration is 5%～60% is prepared, is stirred, be prepared into maceration extract；
(2) high porosity carbon fiber matter heat-barrier material is put in closed mold, vacuumizes 30～60min, then by step (1)
In the maceration extract for preparing be transferred at room temperature in closed mold, 60～120min of vacuum impregnation is fine by the carbon after dipping
Dimension matter heat-barrier material takes out from closed mold, and 2～12h is dried under the conditions of -60 DEG C of air at room temperature；
(3) by the dried carbon fiber matter heat-barrier material of step (2) under inert atmosphere with the heating rate liter of 3～10 DEG C/min
To 170～220 DEG C, solidification 60～180min of crosslinking is then proceeded to the ramp of 2～5 DEG C/min to 900～1400 temperature
DEG C, 60～120min of Pintsch process, cracking is down to room temperature after finishing with the speed of 3～10 DEG C/min；
(4) according to sample density, intensity and ceramic phase content requirement, repeat step (2) and (3) repeatedly, such as 2-10 time, obtain
Low-density infusibility oxidation resistant carbon ceramic composite material.
2. a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material according to claim 1, its feature exists
In：In described step (1), Polymer ceramic precursor includes poly- silicon-carbon alkane, polysilazane, the poly- silicon-carbon alkane containing B element, gathers
One kind in siloxanes.
3. a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material according to claim 1, its feature exists
In：In described step (1), the solvent adopted during prepared polymer ceramics precursor liquid solution is for Polymer ceramic precursor
Good solvent.
4. a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material according to claim 3, its feature exists
In：Described good solvent is the one kind in dimethylbenzene, toluene, benzene, n-hexane, ethanol, tetrahydrofuran, chloroform.
5. a kind of preparation method of low-density infusibility oxidation resistant carbon ceramic composite material according to claim 1, its feature exists
In：In described step (2), high porosity carbon fiber matter heat-barrier material be chopped carbon fiber acupuncture rigidly heat-insulated carbon felt, be chopped
The flexible heat-insulated carbon felt of carbon fiber acupuncture, the heat-insulated carbon felt of rigidity of chopped carbon fiber braiding, chopped carbon fiber weave
One kind in flexible heat-insulated carbon felt, high porosity 3D rigidity carbon bonding thermal insulation tiles, high porosity carbon fiber matter heat-barrier material it is close
Spend for 0.15～0.50g/cm3, porosity is 70%～95%.
6. according to a kind of preparation method of the arbitrary described low-density infusibility oxidation resistant carbon ceramic composite material of Claims 1 to 5, its
It is characterised by：Low-density infusibility oxidation resistant carbon ceramic composite material, ceramic phase mass content between 30%～80%, fibre fractionation
Mass content between 70%～20%, density is in 0.30～1.20g/cm3Between.
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