CN109467457A - Composition utilizes porous carbon fiber heat-barrier material surface high emissivity antioxidant coating and preparation method thereof made from the composition - Google Patents
Composition utilizes porous carbon fiber heat-barrier material surface high emissivity antioxidant coating and preparation method thereof made from the composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5071—Silicides
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
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Abstract
The present invention relates to a kind of composition, utilize porous carbon fiber heat-barrier material surface high emissivity antioxidant coating and preparation method thereof made from the composition.The composition includes following component: transition metal boride, refractory metal silicide, carborundum powder, Polycarbosilane and cerium oxide.The preparation method includes the following steps: to prepare slurry；Slurry is coated to porous carbon fiber heat insulation material；The porous carbon fiber heat-barrier material for being coated with slurry is successively dried, is heat-treated and is sintered, and obtains porous carbon fiber heat-barrier material surface high emissivity antioxidant coating.The composition, which is applied in coating preparation, can reduce sintering temperature, and coating, which is made, has the advantages that emissivity is higher, high-temperature heat conductivity is lower, ultra-high temperature has good stability, and be expected in the thermal protection system applied to hypersonic vehicle.
Description
Technical field
It is made the present invention relates to superhigh temperature heat-barrier material technical field more particularly to a kind of composition, using the composition
Porous carbon fiber heat-barrier material surface high emissivity antioxidant coating and preparation method thereof.
Background technique
Carbon fiber bonding carbon fibre composite is the carbon/carbon compound material of one kind of low density high porosity.It has height
The excellent properties such as the porosity, low-density, lower thermal conductivity, high-temperature stability, optimum is used to manufacture lightweight heat-proof and resistance to ablation is anti-
The matrix or skeleton of hot material, it is also the heat-insulating material in a kind of inert gas environment for being widely used in 2000 DEG C or more.
Although carbon fiber, which bonds carbon fibre composite, has excellent superhigh temperature performance, such as mechanical behavior under high temperature, high
The performances such as warm lower thermal conductivity, but since it is full carbonaceous material, so having a fatal weakness: in air atmosphere, 400
It DEG C begins to aoxidize.This weakness significantly limits its application as high-temperature hot guard system material.At present in carbon
The anti-oxidation aspect of material, surface recombination antioxidant coating are considered as the most effective side for improving carbon-based material oxidation resistance
Method.
SiC base antioxidant coating aoxidizes at high temperature (1400~1600 DEG C) and is capable of forming a layer silicate glassy layer, suppression
External oxygen processed is spread to material internal, and basis material is effectively protected, to show good antioxygenic property, but its
(> 1600 DEG C) are difficult to realize the effective protection to carbon material under medium temperature (700~1200 DEG C) and superhigh temperature aerobic environment.Existing skill
There is the boride (ZrB by addition transition metal in art2、TaB2Or HfB2) scheme that SiC coating is modified, boronation
Object generates liquid B after middle low-temperature oxidation2O3Play the role of to carbon base body in the oxidation protection of middle low temperature it is good, and super
Under high-temperature temperature, the oxide of magnesium-yttrium-transition metal can interact to form M-Si-O complex phase glassy layer again with silicate glass, increase
The stability of strong glassy layer.However, the skill being modified using transition metal boride to SiC coating disclosed in the prior art
Art scheme needs higher sintering temperature in the preparation.
Currently, the method in carbon material surface prepares coating is mainly brushing method, investment, in-situ reaction and plasma
Spray coating method etc..Although plasma spraying method is easy to control the content of boride in the thickness and coating of coating, but required set
Standby condition is harsh, higher cost, and the porosity of coating is higher, and bond strength is poor；Although and investment and in-situ reaction
Have many advantages, such as cost is relatively low, simple and easy, synthesis is mutually uniformly distributed, with matrix compatibility is preferable, interface bond strength is higher,
But the thickness of each component content and coating in coating more difficult to control, simultaneous reactions generally require higher sintering temperature (>
2000℃).By mixing Pyrex prepares coating slurry, the preparation temperature of coating can be reduced by brush coating process, but by
In the presence of a large amount of glass phases, the use temperature of coating is reduced.Polymer cracking SiC coating can obviously reduce the formation of coating
Temperature, but biggish contraction is had in cracking process.
Meanwhile the thermal protection system used as hyperthermal environments, to carbon fiber bonding carbon fibre composite high warm
Conductance has higher requirement, on the one hand requires the carbon fiber skeleton of preparation to have high porosity, reduces heat transfer；It is also desirable to
Material has a high emission coating, the coating of high emissivity can effective heat loss through radiation form by the heat of matrix quickly and efficiently spoke
It is shot out, reduces substrate temperature.
Summary of the invention
The purpose of the present invention is to provide a kind of high emissivity antioxygens for being used to prepare porous carbon fiber heat-barrier material surface
Change coating composition, using the composition preparation porous carbon fiber heat-barrier material surface high emissivity antioxidant coating with
And the preparation method of the high emissivity antioxidant coating on porous carbon fiber heat-barrier material surface.
To achieve the goals above, the present invention provides the following technical scheme that
1, it is anti-to provide a kind of high emissivity for being used to prepare porous carbon fiber heat-barrier material surface for first aspect present invention
The composition of oxide covering, the composition include following component: transition metal boride, refractory metal silicide, silicon carbide
Powder, Polycarbosilane and cerium oxide.
2, composition according to technical solution 1,
In the composition, the mass percentage of each component is as follows:
3, the composition according to technical solution 1 or 2, the transition metal boride are selected from zirconium boride, hafnium boride, boron
It is any one or more of to change tantalum；And/or
It is any one or more of that the refractory metal silicide is selected from molybdenum silicide, tantalum silicide.
4, the composition according to technical solution 1 or 2, the cerium oxide use nano cerium oxide.
5, the composition according to technical solution 4, the nano cerium oxide are prepared using colloidal sol-gel method.
6, the composition according to technical solution 5, the nano cerium oxide are prepared as follows:
Soluble or dissolvable cerium salt is dissolved, catalyst is added and is stirred to react generation colloidal sol；
Colloidal sol is successively dried, roasted and ground, the nano cerium oxide is obtained.
7, the composition according to technical solution 6, the cerium salt are cerous nitrate, and the catalyst is oxalic acid or lemon
Acid；With
The reaction condition of the sol-gel are as follows:
The concentration of the solution obtained after cerous nitrate dissolution is 0.5 to 1mol/L；
The molar ratio of cerous nitrate and catalyst is 1:(1~4)；
The reaction for generating colloidal sol carries out under the conditions of 40 to 80 DEG C of water bath with thermostatic control；
The drying carries out at 80 to 140 DEG C；And/or
The roasting carries out at 500 to 800 DEG C.
8, second aspect of the present invention provides a kind of porous carbon fiber heat-barrier material surface high emissivity antioxidant coating
Preparation method includes the following steps:
(1) the described in any item compositions of technical solution 1 to 7 are mixed with the organic solvent that can dissolve Polycarbosilane,
It is configured to slurry；
(2) slurry is coated to porous carbon fiber heat insulation material；
(3) will through step (2), treated that porous carbon fiber heat-barrier material is successively dried, is heat-treated and is sintered, obtain
To porous carbon fiber heat-barrier material surface high emissivity antioxidant coating.
9, the preparation method according to technical solution 8, the usage amount of the organic solvent meet following condition: You Jirong
The mass percentage of Polycarbosilane is 5 to 30% in agent and the mixed solution of Polycarbosilane.
10, the preparation method according to technical solution 8 or 9, the porous carbon fiber heat-barrier material are viscose base, phenolic aldehyde
The carbon/carbon compound material that base or polyacrylonitrile-radical short carbon fiber are prepared using filter press technique or vacuum filtration method.
11, slurry is coated in porous carbon fiber in step (2) by the preparation method according to technical solution 8 or 9
Further include handling as follows after on heat-barrier material:
Porous carbon fiber heat-barrier material is dried 10 to 50 minutes at 50 to 80 DEG C, is then flattened, is sprayed using spray gun spraying
It is dried 3 to 8 hours after painting at 80 to 100 DEG C.
12, the preparation method according to technical solution 8 or 9, in step (4), the drying at 60 to 90 DEG C into
Row, drying time controlled at 6 to 12 hours；
The heat treatment carries out at 180 to 250 DEG C, and soaking time was controlled at 6 to 24 hours；And/or
The sintering carries out under an inert atmosphere, and sintering temperature is 1100 to 1300 DEG C, and heating rate is 1 to 5 DEG C/min,
Soaking time was controlled at 1 to 3 hour.
13, third aspect present invention provides a kind of porous carbon fiber heat-barrier material surface high emissivity antioxidant coating,
It is made using any one of technical solution 8 to 12 preparation method；Preferably, the high emissivity antioxidant coating with a thickness of
100 to 200 microns.
Beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
Provided by the present invention for preparing the combination of the high emissivity antioxidant coating on porous carbon fiber heat-barrier material surface
In object, cerium oxide inhibits the decaying of oxide covering high temperature emissive rate, improves high emissivity coating spoke in high temperature aerobic environment
The shortcomings that penetrating performance degradation, while using Polycarbosilane for high-temperature agglomerant, with polymer cracking sinter coating, reduce sintering
Temperature.
Porous carbon fiber heat-barrier material provided by the invention surface high emissivity antioxidant coating has emissivity higher, high
Warm the advantages of conductance is lower, ultra-high temperature has good stability.
Preparation method provided by the invention using slurry rinses painting and spraying combine heat treatment process porous carbon fiber every
Hot material surface prepares coating, without using complicated equipment, preparation temperature is lower, and cost is relatively low, and the period is shorter, obtained more
Hole carbon fiber heat insulation material surface high emissivity antioxidant coating ultra-high temperature has good stability, and is expected to fly applied to hypersonic speed
In the thermal protection system of row device.
Detailed description of the invention
Fig. 1 is that the surface SEM of product made from embodiment 1 schemes (500 ×)；
Fig. 2 is that the surface SEM of product made from embodiment 1 schemes (300 ×)；
Fig. 3 is that the side SEM of product made from embodiment 1 schemes (100 ×)；
Fig. 4 is that the side SEM of product made from embodiment 1 schemes (200 ×).
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of high emissivity antioxidant coatings for being used to prepare porous carbon fiber heat-barrier material surface
Composition, the composition include following component: transition metal boride, refractory metal silicide, carborundum powder, Polycarbosilane
And cerium oxide.
In composition provided by the invention, the emissivity of coating is not only can be improved in refractory metal silicide, but also
It is improved the stability of coating at high temperature；Oxide ceramic material of the cerium oxide as high-melting-point (2600 DEG C),
1000~2000 DEG C of emissivity are stablized, and do not decay, can inhibit the decaying of oxide covering high temperature emissive rate using it, improve
High emissivity coating is in high temperature aerobic environment the shortcomings that radiance decaying；Use Polycarbosilane for high-temperature agglomerant simultaneously,
With polymer cracking sinter coating, sintering temperature is reduced.
In some preferred embodiments, the mass percentage of each component is as follows:
Transition metal boride: 10 to 30%, for example, can be 10%, 15%, 20%, 25% or 30%；
Refractory metal silicide: 15 to 45%, for example, can for 15%, 20%, 25%, 30%, 35%, 40% or
45%；
Carborundum powder: 15 to 25%, for example, can be 15%, 20% or 25%；
Polycarbosilane: 10 to 20%, for example, can be 10%, 15% or 20%；
Cerium oxide: 5 to 10%, for example, can be 5%, 6%, 7%, 8%, 9% or 10%.
In some preferred embodiments, the transition metal boride is selected from zirconium boride (ZrB2), hafnium boride
(HfB2), tantalum boride (TaB2) any one or more of.
In some preferred embodiments, the refractory metal silicide is selected from molybdenum silicide (MoSi2), tantalum silicide
(TaSi2) any one or more of.It should be noted that term " infusibility " refers to fusing point at 1650 DEG C or more.
In some preferred embodiments, the cerium oxide uses nano cerium oxide, which can be with
It is prepared using sol-gel method.Specifically, the nano cerium oxide can be prepared as follows:
Soluble or dissolvable cerium salt is dissolved, catalyst is added and is stirred to react generation colloidal sol；The cerium salt can be nitric acid
Cerium, the catalyst can be oxalic acid or citric acid, and the reaction condition of the sol-gel is preferred are as follows: after cerous nitrate dissolution
The concentration of the solution arrived be 0.5 to 1mol/L, for example, can for 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L,
0.9mol/L or 1mol/L；The molar ratio of cerous nitrate and catalyst is 1:(1~4), for example, can be 1:1,1:2,1:3 or 1:
4；Generate water bath with thermostatic control item of the reaction 40 to 80 DEG C (for example, can be 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C) of colloidal sol
It is carried out under part；
Colloidal sol obtained is successively dried, roasted and ground, the nano cerium oxide is obtained.The drying can be with
It is carried out under 80 to 140 DEG C (for example, can be 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C or 140 DEG C), it is described
Roasting can carry out under 500 to 800 DEG C (for example, can be 500 DEG C, 600 DEG C, 700 DEG C or 800 DEG C).
Readily soluble, the solvable size for describing substance solvability in solvent that the present invention mentions.It and the substance
(20 DEG C, solvent is water) of solubility have following relationship:
| Dissolubility | It is readily soluble | It is solvable |
| Solubility (20 DEG C) | > 10g | 1~10g |
Present invention provides a kind of preparation method of porous carbon fiber heat-barrier material surface high emissivity antioxidant coating,
This method rinses painting using slurry and spraying combines heat treatment process in porous carbon fiber heat-barrier material surface prepares coating, is not necessarily to
Using complicated equipment, preparation temperature is lower, and cost is relatively low, and the period is shorter, and porous carbon fiber heat-barrier material obtained surface is high
Emissivity antioxidant coating ultra-high temperature has good stability, and is expected in the thermal protection system applied to hypersonic vehicle.
Specifically, which includes the following steps:
(1) it is formulated for the slurry brushed
Above-mentioned composition provided by the invention is mixed with the organic solvent that can dissolve Polycarbosilane, is configured to slurry；
In order to obtain the slurry of suitable viscosity, the usage amount of the organic solvent meets following condition: organic solvent and Polycarbosilane are mixed
The mass percentage of Polycarbosilane is 5 to 30% in solution after conjunction, for example, can for 5%, 10%, 15%, 20%,
25% or 30%.
The present invention does not limit the type of organic solvent particularly, and it is preferable to employ dimethylbenzene or divinylbenzenes.
During preparing slurry, first Polycarbosilane (PCS) can be ground to powdered, then be dissolved in organic molten
The PCS solution that PCS content (mass percentage) is 5~30% is configured in agent, then by the other components in composition
(transition metal boride, carborundum powder and cerium oxide) is added in PCS solution, is uniformly mixed, is obtained the slurry for brushing.
In some way of example, mixed method can use ball-milling method.It (include transition metal by above-mentioned PCS solution
Boride, carborundum powder, Polycarbosilane and cerium oxide) it is put into ball-milling device, using zirconia ball as abrasive media, ball grinding stirring
(for example, 6 to 24 hours) for a period of time obtain uniform slurry.
(2) slurry is coated to porous carbon fiber heat insulation material
In this step, can using brushing side by the slurry that step (1) is prepared be uniformly applied to porous carbon fiber every
On hot material.It can be by porous carbon fiber heat-barrier material 50 to 80 after brushing for the planarization for being further ensured that coating
10 to 50 minutes are dried (for example, can be 10 minutes, 20 points under DEG C (for example, can be 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C)
Clock, 30 minutes, 40 minutes or 50 minutes), it is then flattened using spray gun spraying, at 80 to 100 DEG C (for example, can be with after spraying
It is 80 DEG C, 90 DEG C or 100 DEG C) 3 to 8 hours (3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours) of drying, porous
Carbon fiber heat insulation material surface forms initialization layer.
In this step, porous carbon fiber heat-barrier material used is preferably that viscose base, phenolic aldehyde base or polyacrylonitrile-radical are short
Cut the carbon/carbon compound material that Carbon fibe is prepared using filter press technique or vacuum filtration method.Preparation process can use existing preparation
Method, to it, it will not be described at this by the present invention.Before the coating slurry on porous carbon fiber heat-barrier material, can first by
Porous carbon fiber heat-barrier material is cut into the material that compound size requires, and is then beaten using different roughness sand paper it
Mill, is cleaned by ultrasonic and is dried again after polishing.
(3) synthetic coating
Will through step (2), treated that porous carbon fiber heat-barrier material is successively dried, is heat-treated and is sintered, obtain more
Hole carbon fiber heat insulation material surface high emissivity antioxidant coating.
In some preferred implementation methods, the drying is at 60 to 90 DEG C (for example, can be 60 DEG C, 70 DEG C, 80 DEG C
Or 90 DEG C) under carry out, drying time control 6 to 12 hours (for example, can for 6 hours, 7 hours, 8 hours, 9 hours, it is 10 small
When, 11 hours or 12 hours)；
The heat treatment is at 180 to 250 DEG C (for example, can be 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230
DEG C, 240 DEG C or 250 DEG C) under carry out, soaking time control 6 to 24 hours (for example, can for 6 hours, 7 hours, 8 hours,
9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, it is 19 small
When, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours)；
The sintering carries out under inert atmosphere (such as argon gas), and sintering temperature is 1100 to 1300 DEG C (for example, can be
1100 DEG C, 1200 DEG C or 1300 DEG C), heating rate be 1 to 5 DEG C/min (for example, can for 1 DEG C/min, 2 DEG C/min, 3 DEG C/
Min, 4 DEG C/min or 5 DEG C/min), soaking time control was at 1 to 3 hour (for example, can be 1 hour, 2 hours or 3 hours).
The present invention also provides a kind of porous carbon fiber heat-barrier material surface high emissivity antioxidant coatings.
The coating using above-mentioned preparation method provided by the invention be made, have emissivity is higher, high-temperature heat conductivity is lower,
The advantages of ultra-high temperature has good stability.Preferably, the high emissivity antioxidant coating with a thickness of 100 to 200 microns, example
It such as, can be 100 microns, 150 microns or 200 microns.
The following are the embodiments that the present invention enumerates.
Embodiment 1
(1) cerous nitrate magnetic agitation is dissolved in deionized water, cerium oxide concentration 0.5mol/L.It is to urge with citric acid
The molar ratio of agent, cerous nitrate and citric acid is 1:2, and gel is made in 60 DEG C of stirring in water bath 3h.By gel obtained at 120 DEG C
Then lower dry 12h roasts 2h at 500 DEG C again, ball milling, which is sieved, is made nano cerium oxide.
(2) porous carbon fiber heat-barrier material is cut into 3.0cm × 3.0cm × 1.0cm fiberboard, and through 500 mesh, 1000
Mesh, 2000 mesh, 3000 mesh SiC sand paper polish flat, and are cleaned by ultrasonic 20min, in 80 DEG C of drying for standby of baking oven.
(3) by Polycarbosilane grind into powder, Polycarbosilane (PCS) powder after grinding is dissolved into xylene solution
In, it is configured to PCS solution, the PCS content in solution is 10% (mass percentage)；By hafnium boride (HfB2), molybdenum silicide
(MoSi2), silicon carbide (SiC), cerium oxide (CeO2) be added in Polycarbosilane (PCS) solution.Wherein hafnium boride (HfB2), silicon
Change molybdenum (MoSi2), silicon carbide (SiC), Polycarbosilane (PCS) and cerium oxide (CeO2) mass percentage be respectively as follows: 20%,
35%, 20%, 15%, 10%.Above-mentioned Polycarbosilane solution is put into ball-milling device and is ground, is grinding with zirconia ball
Medium ball grinding stirring 6 hours, forms slurry uniform, that viscosity is suitable.
(4) use brushing method, by the slurry of preparation, using hairbrush be coated in porous carbon fiber that step (2) are handled well every
On hot material, dries 30 minutes for 60 DEG C, then flattened using spray gun 0.25MPa air spraying, after spraying in an oven after coating
It is dried 4 hours at 80 DEG C, forms initialization layer on porous carbon fiber heat-barrier material surface.
It (5) will be through step (4) treated material 90 DEG C of dryings, 6 hours removal organic solvents in an oven, then at 240 DEG C
Lower crosslinking 12 hours is warming up to 1200 DEG C then under argon atmosphere, and heating rate is 5 DEG C/min, and cracking sintering 2 is small
When, cool down later with furnace, obtain high emissivity antioxidant coating, shape appearance figure is shown in Fig. 1, Fig. 2, Fig. 3 and Fig. 4.
Embodiment 2
(1) cerous nitrate magnetic agitation is dissolved in deionized water, cerium oxide concentration 1mol/L.It is catalysis with citric acid
The molar ratio of agent, cerous nitrate and citric acid is 1:2, and gel is made in 60 DEG C of stirring in water bath 4h.By gel obtained at 120 DEG C
Then dry 12h roasts 2h at 500 DEG C again, ball milling, which is sieved, is made nano cerium oxide.
(2) porous carbon fiber heat-barrier material is cut into 3.0cm × 3.0cm × 1.0cm fiberboard, and through 500 mesh, 1000
Mesh, 2000 mesh, 3000 mesh SiC sand paper polish flat, and are cleaned by ultrasonic 20min, in 80 DEG C of drying for standby of baking oven.
(3) by Polycarbosilane grind into powder, Polycarbosilane (PCS) powder after grinding is dissolved into xylene solution
In, it is configured to PCS solution, the PCS content in solution is 10% (mass percentage)；By hafnium boride (HfB2), molybdenum silicide
(MoSi2), silicon carbide (SiC), cerium oxide (CeO2) be added in Polycarbosilane (PCS) solution.Wherein hafnium boride (HfB2), silicon
Change molybdenum (MoSi2), silicon carbide (SiC), Polycarbosilane (PCS) and cerium oxide (CeO2) mass percentage be respectively 25%,
30%, 20%, 15%, 10%.Above-mentioned Polycarbosilane solution is put into ball-milling device and is ground, is grinding with zirconia ball
Medium ball grinding stirring 6 hours, forms slurry uniform, that viscosity is suitable.
(4) use brushing method, by the slurry of preparation, using hairbrush be coated in porous carbon fiber that step (2) are handled well every
On hot material, dries 30 minutes for 60 DEG C, then flattened using spray gun 0.25MPa air spraying, after spraying in an oven after coating
It is dried 4 hours at 80 DEG C, forms initialization layer on porous carbon fiber heat-barrier material surface.
It (5) will be through step (4) treated material 90 DEG C of dryings, 6 hours removal organic solvents in an oven, then at 240 DEG C
Lower crosslinking 12 hours is warming up to 1300 DEG C then under argon atmosphere, and heating rate is 5 DEG C/min, and cracking sintering 2 is small
When, cool down later with furnace, obtains high emissivity antioxidant coating.
Embodiment 3
Step is substantially the same with embodiment 1, the difference is that:
In step (3), the mass percentage of each component is as follows:
Embodiment 4
Step is substantially the same with embodiment 1, the difference is that:
In step (3), the mass percentage of each component is as follows:
Embodiment 5
Step is substantially the same with embodiment 1, the difference is that:
In step (3), the mass percentage of each component is as follows:
Embodiment 6
Step is substantially the same with embodiment 1, the difference is that: in step (3), do not add cerium oxide.
Embodiment 7
Step is substantially the same with embodiment 1, the difference is that: in step (3), the mass percentage of each component
It is as follows:
Embodiment 8
Step is substantially the same with embodiment 1, the difference is that: in step (3), the mass percentage of each component
It is as follows:
Embodiment 9
Step is substantially the same with embodiment 1, the difference is that: in step (3), the mass percentage of each component
It is as follows:
Embodiment 10
Step is substantially the same with embodiment 1, the difference is that:
In step (3), the mass percentage of each component is as follows:
Emissivity detection
Emissivity, also known as radiance refer under the conditions of certain temperature, and other conditions are also identical, actual object with should
At a temperature of black body radiation emittance ratio, calculation method is shown in following formula:
In formula, Mh(T) respectively refer to that other conditions are identical with M (T), the radiation of black matrix and actual object under the conditions of temperature T
Emittance.
The value range of emissivity is greater than 0 less than 1, and meaning indicates the radianting capacity of actual object and approaching for black matrix
Degree.It is stronger to represent its radianting capacity closer to 1 for the size of emissivity.The big material of emissivity is it is desirable that the production obtained
Product.
Testing result is shown in Table 1.
Table 1
The emissivity that can be seen that coating made from embodiment 1 to embodiment 5 from above-mentioned testing result can reach 0.85
Or more.What embodiment 6 to embodiment 10 had can not obtain workable coating, although some coatings can also have certain hair
Rate is penetrated, but its effect is not as good as embodiment 1 to embodiment 5.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of composition for the high emissivity antioxidant coating for being used to prepare porous carbon fiber heat-barrier material surface, feature exist
In the composition includes following component: transition metal boride, refractory metal silicide, carborundum powder, Polycarbosilane and oxygen
Change cerium.
2. composition according to claim 1, which is characterized in that in the composition, the quality percentage of each component
Content is as follows:
3. composition according to claim 1 or 2, which is characterized in that the transition metal boride is selected from zirconium boride, boron
It is any one or more of to change hafnium, tantalum boride；And/or
It is any one or more of that the refractory metal silicide is selected from molybdenum silicide, tantalum silicide.
4. composition according to claim 1 or 2, which is characterized in that the cerium oxide uses nano cerium oxide；
Preferably, the nano cerium oxide is prepared using sol-gel method；
Preferably, the nano cerium oxide is prepared as follows:
Soluble or dissolvable cerium salt is dissolved, catalyst is added and is stirred to react generation colloidal sol；
Colloidal sol is successively dried, roasted and ground, the nano cerium oxide is obtained.
5. composition according to claim 4, which is characterized in that the cerium salt is cerous nitrate, and the catalyst is oxalic acid
Or citric acid；With
The reaction condition of the sol-gel are as follows:
The concentration of the solution obtained after cerous nitrate dissolution is 0.5 to 1mol/L；
The molar ratio of cerous nitrate and catalyst is 1:(1~4)；
The reaction for generating colloidal sol carries out under the conditions of 40 to 80 DEG C of water bath with thermostatic control；
The drying carries out at 80 to 140 DEG C；And/or
The roasting carries out at 500 to 800 DEG C.
6. a kind of preparation method of porous carbon fiber heat-barrier material surface high emissivity antioxidant coating, which is characterized in that including
Following steps:
(1) composition described in any one of claim 1 to 5 is mixed with the organic solvent that can dissolve Polycarbosilane, is prepared
At slurry；Preferably, the usage amount of the organic solvent meets following condition: organic solvent and the mixed solution of Polycarbosilane
The mass percentage of middle Polycarbosilane is 5 to 30%；
(2) slurry is coated to porous carbon fiber heat insulation material；
(3) the porous carbon fiber heat-barrier material for being coated with slurry is successively dried, is heat-treated and is sintered, and obtains porous carbon fiber
Tie up heat-barrier material surface high emissivity antioxidant coating.
7. preparation method according to claim 6, which is characterized in that the porous carbon fiber heat-barrier material be viscose base,
The carbon/carbon compound material that phenolic aldehyde base or polyacrylonitrile-radical short carbon fiber are prepared using filter press technique or vacuum filtration method.
8. preparation method according to claim 6, which is characterized in that in step (2), slurry is coated in porous carbon fiber
Further include handling as follows after tieing up on heat-barrier material:
Porous carbon fiber heat-barrier material is dried 10 to 50 minutes at 50 to 80 DEG C, is then flattened using spray gun spraying, after spraying
It is dried 3 to 8 hours at 80 to 100 DEG C.
9. preparation method according to claim 6, which is characterized in that in step (4), the drying is at 60 to 90 DEG C
It carries out, drying time controlled at 6 to 12 hours；
The heat treatment carries out at 180 to 250 DEG C, and soaking time was controlled at 6 to 24 hours；And/or
The sintering carries out under an inert atmosphere, and sintering temperature is 1100 to 1300 DEG C, and heating rate is 1 to 5 DEG C/min, heat preservation
Time controlled at 1 to 3 hour.
10. a kind of porous carbon fiber heat-barrier material surface high emissivity antioxidant coating, which is characterized in that use claim 6
It is made to any one of 9 preparation methods；Preferably, the high emissivity antioxidant coating with a thickness of 100 to 200 microns.
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| CN113213973A (en) * | 2021-05-25 | 2021-08-06 | 哈尔滨工业大学 | Method for controlling sintering atmosphere of high-emissivity thermal protection coating |
| CN113788707A (en) * | 2021-10-09 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Cerium-modified antioxidant ceramic matrix composite and preparation method thereof |
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