CN110115961A - A kind of method improving charcoal-aero gel antioxygenic property and thus obtained modified charcoal-aero gel - Google Patents
A kind of method improving charcoal-aero gel antioxygenic property and thus obtained modified charcoal-aero gel Download PDFInfo
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- CN110115961A CN110115961A CN201910438900.7A CN201910438900A CN110115961A CN 110115961 A CN110115961 A CN 110115961A CN 201910438900 A CN201910438900 A CN 201910438900A CN 110115961 A CN110115961 A CN 110115961A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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Abstract
The present invention relates to a kind of method for improving charcoal-aero gel antioxygenic property and thus obtained modified charcoal-aero gels.The method are as follows: charcoal-aero gel is carried out by embedding using mixed powder and carries out high-temperature process under inert atmosphere, first layer coating is prepared on the surface of charcoal-aero gel, mixed powder includes silicon powder 55~85%, carbon dust 5~25% and alumina powder 5~20% by percentage to the quality, and the partial size of silicon powder, carbon dust and alumina powder is 300~500 mesh；Using trichloromethyl silane as reaction gas, it is carrier gas and using hydrogen and argon gas as diluent gas using argon gas, second layer coating is prepared on the basis of first layer coating by chemical vapour deposition technique, gradient antioxidant coating thus is made to improve the antioxygenic property of charcoal-aero gel on the surface of charcoal-aero gel.The excellent charcoal-aero gel of antioxygenic property of gradient coating protection has been made in the method for the present invention, and the antioxygenic property compared to untreated charcoal-aero gel improves 30% or more.
Description
Technical field
The invention belongs to carbon aerogel material technical field more particularly to a kind of sides for improving charcoal-aero gel antioxygenic property
Method and thus obtained modified charcoal-aero gel.
Background technique
The development of space technology proposes higher demand to high temperature heat-resistant protective materials, efficiently, the high temperature resistant of lightweight every
Hot material is the key that various thermal protection systems.Super burn engine operating temperature is high, and the requirement to heat-barrier material is especially harsh:
The material heat-insulated applied to engine has first had to good high temperature (>=2000 DEG C) stability, also to there is excellent thermal insulation
Energy, lower density and good processing performance obtain reliable heat insulation with lesser thickness and lighter weight.
Aerogel material is heat-barrier material best at present, it is mutually to be built up to constitute by colloidal particle or the high-polymer molecule
A kind of nanoporous solid material with network structure, due to its aperture (< 50nm) be less than air molecule it is average from
There is extremely low gaseous heat conduction without cross-ventilation by journey (~70nm), thus in aerogel pores；Aeroge has simultaneously
High porosity, volume ratio shared by solid is very low, and solid-state heat transfer is also very low, and therefore, aeroge is ideal efficient light
Heat-barrier material has broad application prospects in heat-insulated field.What technology was most mature in current existing aerogel material is two
Silica aerogel, but it is no more than 800 DEG C using temperature, can not make since nanostructure is destroyed at a higher temperature
With.Charcoal-aero gel high temperature resistance in various aeroges is best (>=2000 DEG C), in High Mach number aircraft thermal protection field
With the superiority that can not be substituted.
In practical application, high temperature aerobic environment causes carbon aerogel material that serious oxidative phenomena occurs.This shadow that is bound to
Heat resistance when sound carbon aerogel material is long has about the research for improving charcoal-aero gel antioxygenic property method important thus
Meaning.
Charcoal-aero gel (Chinese patent application CN1891622A and CN101468795A) mainly passes through phenol and aldehyde at this stage
It by the method for sol-gel, is further dried obtained from carbonization, but its application at present is mainly by its antioxygenic property difference
Limitation.
Summary of the invention
The purpose of the invention is to provide a kind of method of charcoal-aero gel antioxygenic property and thus obtained of improving
Modified charcoal-aero gel, to solve the problems, such as that existing charcoal-aero gel antioxygenic property is poor.
To achieve the goals above, the present invention provides a kind of side for improving charcoal-aero gel antioxygenic property in first aspect
Method, described method includes following steps:
(1) charcoal-aero gel embed using mixed powder and carry out high-temperature process under inert atmosphere protection, described
The surface of charcoal-aero gel prepares first layer coating, and the mixed powder includes silicon powder 55~85%, carbon dust 5 by percentage to the quality
~25% and alumina powder 5~20%, the partial size of the silicon powder, the carbon dust and the alumina powder is 300~500 mesh；With
(2) it is carrier gas and using hydrogen and argon gas as diluent gas using argon gas using trichloromethyl silane as reaction gas, leads to
It crosses chemical vapour deposition technique and prepares the second layer coating on the basis of first layer coating prepared by step (1), thus in institute
The surface for stating charcoal-aero gel is made by the first layer coating and the coat composed gradient antioxidant coating of the second layer to mention
The antioxygenic property of high charcoal-aero gel.
Preferably, the mixed powder also includes the silicon dioxide powder that mass percent is 0~5%, the silicon dioxide powder
Partial size be 300~500 mesh.
Preferably, the mixed powder also includes the boron oxide powder that mass percent is 0~5%, the grain of the boron oxide powder
Diameter is 300~500 mesh.
Preferably, the mixed powder is by silicon powder 55~85%, carbon dust 5~20% and aluminium oxide by percentage to the quality
Powder 5~15%, silicon dioxide powder 0~5% and boron oxide powder 0~5% form.
Preferably, the inert atmosphere is argon atmosphere or nitrogen atmosphere.
Preferably, the temperature of the high-temperature process is 1300~1600 DEG C, time of the high-temperature process is 30~
60min。
Preferably, it is prepared on the basis of by chemical vapour deposition technique in the first layer coating prepared by step (1)
During the second layer coating, the flow of the trichloromethyl silane is 60~200g/h, and the flow of the hydrogen is 0.2
~1.5m3The flow of/h and/or the argon gas is 0.5~2m3/h。
Preferably, in step (2), the temperature of chemical vapor deposition is 950~1100 DEG C, the time of chemical vapor deposition
For 20~100h.
Preferably, in step (2), trichloromethyl silane is brought into chemical vapor deposition stove to lead to by bubbling mode
It crosses chemical vapour deposition technique and prepares the second layer coating on the basis of first layer coating prepared by step (1).
The present invention provides modified charcoal-aero gel made from the method as the present invention described in first aspect in second aspect,
The modified charcoal-aero gel includes the gradient antioxidant coating of charcoal-aero gel with the surface for being formed in the charcoal-aero gel.
The present invention at least have compared with prior art it is following the utility model has the advantages that
(1) the method for the present invention first passage is in the surface of charcoal-aero gel preparation gradient antioxidant coating to improve charcoal-aero gel
Antioxygenic property, overcome it has been generally acknowledged that charcoal-aero gel be nanoporous solid material, the meeting in coating preparation process
Causing powder material to enter in the nano-porous structure of charcoal-aero gel and causes the nanostructure of charcoal-aero gel to destroy to be bound to
It will affect the technology prejudice of its heat resistance and antioxygenic property.
(2) mixed powder in the method for the present invention include silicon powder 55~85% by percentage to the quality, carbon dust 5~
25% and alumina powder 5~20%, the partial size of the silicon powder, the carbon dust and the alumina powder is 300~500 mesh, this hair
The bright mixed powder using rationally composition, rational proportion and reasonable partial size is prepared for the on the surface of charcoal-aero gel by investment
One layer of coating can effectively avoid mixed powder from entering in the internal nanostructure of the charcoal-aero gel, and pass through chemical gaseous phase
Sedimentation is prepared for second layer coating (SiC coating) on the basis of first layer coating, is applied to be made by the first layer
The collective effect of layer and the coat composed gradient antioxidant coating of the second layer, the first layer coating and second layer coating is aobvious
The antioxygenic property for improving charcoal-aero gel is write, the excellent modification charcoal-aero gel of antioxygenic property has been made.
(3) present invention is had found by Muffle furnace high temperature aerobic environment certification test, under the same terms, has gradient anti-oxidant
The charcoal-aero gel (modified charcoal-aero gel) of coating improves 30% or more than the antioxygenic property of untreated charcoal-aero gel.
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, it is clear that and 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 method for improving charcoal-aero gel antioxygenic property in first aspect, and the method includes such as
Lower step:
(1) charcoal-aero gel (carbon aerogels) is carried out by embedding using mixed powder and is carried out at high temperature under inert atmosphere protection
Reason, prepares first layer coating (first layer antioxidant coating) on the surface of the charcoal-aero gel, and the mixed powder includes with quality
Silicon powder (Si powder) 55~85% (such as 55%, 60%, 65%, 70%, 75%, 80% or 85%), the carbon dust (C of percentages
Powder) 5~25% (such as 5%, 10%, 15%, 20% or 25%) and alumina powder (Al2O3Powder) 5~20% (such as 5%,
10%, 15% or 20%), the partial size of the silicon powder, the carbon dust and the alumina powder is 300~500 mesh (25~48 μm)；
Specifically, such as by high-purity (>=99.5%) Si powder, C powder and Al2O3Powder, 3~6h of ball milling in ball mill, crosses 300- respectively
500 meshes, respectively obtaining partial size is Si powder, the C powder and the Al described in 300~500 purposes2O3Powder, then according to several powder
Body mass ratio is Si:C:Al2O3=55-85%:5-25%:5-20% is mixed, and uniform powder is fallen in graphite crucible,
Charcoal-aero gel fritter is embedded, high-temperature process is carried out in vacuum drying oven inert atmosphere protection, the first layer coating is made.
(2) it is carrier gas and using hydrogen and argon gas as diluent gas using argon gas using trichloromethyl silane as reaction gas, leads to
Chemical vapour deposition technique is crossed to prepare the second layer coating on the basis of first layer coating prepared by step (1) (second layer is anti-
Oxide covering), thus it is made coat composed by the first layer coating and the second layer on the surface of the charcoal-aero gel
Gradient antioxidant coating is to improve the antioxygenic property of charcoal-aero gel.
Although have in the prior art much about on the composite materials such as C/C prepare antioxidant coating to improve composite wood
The report of the antioxygenic property of material, but during preparing these antioxidant coatings, powder material can enter the composite woods such as C/C
The inside of material, and the structure of composite materials such as carbon aerogel material and C/C is different, charcoal-aero gel is nanoporous solid material
Material, thus usually will be considered that if preparing antioxidant coating on charcoal-aero gel, powder can be led in coating preparation process
Raw material, which enters, in the nano-porous structure of charcoal-aero gel and causes the nanostructure of charcoal-aero gel to destroy to be unfavorable for
Promoted charcoal-aero gel it is long when heat resistance and antioxygenic property, this is also to be there are no in the prior art about in charcoal-aero gel
Material surface prepares the reason of relevant report of antioxidant coating；And the method for the present invention first passage is in the surface system of charcoal-aero gel
It is standby to be different from the gradient antioxidant coating of existing antioxidant coating to improve the antioxygenic property of charcoal-aero gel, it overcomes and usually recognizes
For charcoal-aero gel be nanoporous solid material, will lead to powder material in coating preparation process and enter charcoal-aero gel
The nanostructure of charcoal-aero gel is caused to destroy the heatproof that will certainly be unfavorable for promoting charcoal-aero gel in nano-porous structure
The technology prejudice of performance and antioxygenic property.
The mixed powder in the method for the present invention includes silicon powder 55~85%, carbon dust 5~25% by percentage to the quality
Partial size with alumina powder 5~20%, the silicon powder, the carbon dust and the alumina powder is 300~500 mesh, and the present invention adopts
It by investment is only to be prepared for the on the surface of charcoal-aero gel with the mixed powder of reasonable composition, rational proportion and reasonable partial size
One layer of coating while so that first layer coating improves the antioxygenic property of charcoal-aero gel to a certain extent, can effectively be kept away
Exempt from micron-sized mixed powder to enter in the internal nanostructure of the charcoal-aero gel, and by chemical vapour deposition technique first
It is prepared for second layer coating (SiC layer) on the basis of layer coating, to be made by investment and vapour deposition process by described
First layer coating and the coat composed gradient antioxidant coating of the second layer, the first layer coating and second layer coating are total to
Same-action significantly improves the antioxygenic property of charcoal-aero gel, and the excellent modification charcoal-aero gel of antioxygenic property has been made；In addition,
The inventors discovered that being unfavorable for being made when the partial size for each ingredient powder that mixed powder includes is not between 300~500 mesh
The excellent modification charcoal-aero gel of antioxygenic property.The present invention passes through the discovery of Muffle furnace high temperature aerobic environment certification test, identical item
Under part, the charcoal-aero gel (modified charcoal-aero gel) with gradient antioxidant coating is than the antioxygenic property of untreated charcoal-aero gel
Improve 30% or more.
According to some preferred embodiments, the mixed powder also include mass percent be 0~5% (such as 0%,
1%, 2%, 3%, 4% or 5%) be preferably 1~5% silicon dioxide powder (SiO2Powder), the partial size of the silicon dioxide powder is
300~500 mesh.
According to some preferred embodiments, the mixed powder also include mass percent be 0~5% (such as 0%,
1%, 2%, 3%, 4% or 5%) be preferably 1~5% boron oxide powder (B2O3Powder), the partial size of the boron oxide powder is 300~
500 mesh.
According to some preferred embodiments, the mixed powder by by percentage to the quality silicon powder 55~85% (such as
55%, 60%, 65%, 70%, 75%, 80% or 85%), carbon dust 5~20% (such as 5%, 10%, 15% or 20%) and
Alumina powder 5~15% (such as 5%, 10% or 15%), silicon dioxide powder 0~5% (such as 0%, 1%, 2%, 3%, 4%
Or it 5%) is formed with boron oxide powder 0~5% (such as 0%, 1%, 2%, 3%, 4% or 5%).The present inventor is by a large amount of examination
It issues after examination and approval now, the component and proportion of the preferably described mixed powder are Si:C:Al2O3: SiO2: B2O3=55~85%:5~20%:5
~15%:0~5%:0~5% can so further avoid micron-sized mixed powder into the inside of charcoal-aero gel nanometer
In structure, while it can also be further ensured that the more excellent charcoal-aero gel with gradient antioxidant coating of obtained antioxygenic property
(modified charcoal-aero gel).
According to some preferred embodiments, the mixed powder is by silicon powder 55~85%, carbon dust by percentage to the quality
5~20% and alumina powder 5~15%, silicon dioxide powder 1~5% and boron oxide powder 1~5% form.
According to some preferred embodiments, the inert atmosphere is argon atmosphere or nitrogen atmosphere.
According to some preferred embodiments, the temperature of the high-temperature process be 1300~1600 DEG C (such as 1300 DEG C,
1350 DEG C, 1400 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C or 1600 DEG C), the time of the high-temperature process is 30~60min (example
Such as 30,35,40,45,50,55 or 60min).The present inventor is by largely testing and groping to find, preferably in indifferent gas
30~60min of high-temperature process is carried out in atmosphere at 1300~1600 DEG C and is more preferably 30~40min, can so be further ensured that institute
The nanostructure for stating charcoal-aero gel is not damaged in embedding process, and it is excellent to be so more advantageous to the obtained antioxygenic property of guarantee
Charcoal-aero gel with gradient antioxidant coating.
According to some specific embodiments, step (1) are as follows: be Si powder, the C of high-purity (>=99.5%) by purity
Powder, Al2O3Powder, SiO2Powder, B2O3The powders such as powder, 3~6h of ball milling in ball mill cross 300~500 meshes, then according to several
Powder quality ratio is Si:C:Al2O3: SiO2: B2O3=55~85%:5~20%:5~15%:0~5%:0~5%, will be equal
Even powder falls in graphite crucible, charcoal-aero gel fritter is embedded, 1300~1600 DEG C of high-temperature process in argon atmosphere
30min prepares first layer coating.
According to some preferred embodiments, in the first layer prepared by chemical vapour deposition technique in step (1)
During preparing the second layer coating on the basis of coating, the flow of the trichloromethyl silane is 60~200g/h (example
Such as 60,70,80,90,100,110,120,130,140,150,160,170,180,190 or 200g/h), the stream of the hydrogen
Amount is 0.2~1.5m3/ h (such as 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4 or
1.5m3/ h) and/or the argon gas flow be 0.5~2m3/ h (such as 0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,
1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2.0m3/h).The present invention is preferably to be by the flow control of trichloromethyl silane
The flow control of 60~200g/h, hydrogen are 0.2~1.5m3The flow control of/h and argon gas is 0.5~2m3/ h, so can be into
One step controls reacting gas concentration, realizes the control to SiC coating (coat of silicon carbide).
According to some preferred embodiments, in step (2), the temperature of chemical vapor deposition is 950~1100 DEG C of (examples
Such as 950 DEG C, 1000 DEG C, 1050 DEG C or 1100 DEG C), the time of chemical vapor deposition be 20~100h (such as 20,30,40,50,
60,70,80,90 or 100h).
According to some preferred embodiments, in step (2), chemistry into is brought trichloromethyl silane by bubbling mode
With described in being prepared on the basis of the first layer coating prepared by step (1) by chemical vapour deposition technique in gaseous phase deposition stove
Second layer coating.
According to some specific embodiments, step (2) are as follows: using trichloromethyl silane as raw material (reaction gas), stream
Amount is 60~200g/h, and using argon gas as carrier gas, hydrogen and argon gas are diluent gas, and the flow of hydrogen and argon gas is respectively 0.2
~1.5m3/ h and 0.5~2m3/ h is brought trichloromethyl silane in reaction chamber by bubbling mode, in chemical vapor deposition stove
At interior 950~1100 DEG C, 20~100h is deposited, i.e., prepares the second layer coating on the basis of first layer coating of charcoal-aero gel.
According to some preferred embodiments, the first layer coating with a thickness of 30~50 μm, the second layer coating
With a thickness of 10~30 μm.In the present invention, it is preferred to be the first layer coating with a thickness of 30~50 μm, and described second
Layer coating with a thickness of 10~30 μm so that the thickness ratio SiC coating layer thickness of the first layer coating is thick, can guarantee the in this way
One layer of coating can protect charcoal-aero gel, prevent SiC coating from entering inside it, and second layer SiC coating layer thickness is relatively thin,
Primarily to the antioxygenic property of enhancing first layer coating.
The present invention provides modified charcoal-aero gel made from the method as the present invention described in first aspect in second aspect,
The modified charcoal-aero gel includes the gradient antioxidant coating of charcoal-aero gel with the surface for being formed in the charcoal-aero gel.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
1. by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder, SiO2Powder, B2O3Powder powder, the ball milling in ball mill
6h crosses 300 meshes, is then Si:C:Al according to several powder quality ratios2O3: SiO2: B2O3=55%:20%:15%:5%:
5% is uniformly mixed, and uniform powder is fallen in graphite crucible, charcoal-aero gel fritter is embedded, 1300 in argon atmosphere
DEG C high-temperature process 30min, prepares the first layer coating with a thickness of 30 μm.
2. flow 70g/h, using argon gas as carrier gas, hydrogen and argon gas are carrier gas using trichloromethyl silane as raw material
The flow of body, hydrogen and argon gas is respectively 0.2m3/ h and 0.5m3/ h brings trichloromethyl silane into reaction by bubbling mode
In room, in chemical vapor deposition stove at 950 DEG C, 50h is deposited, i.e., on the basis of the first layer coating of charcoal-aero gel surface preparation
The charcoal-aero gel (modified charcoal-aero gel) with gradient antioxidant coating is made with a thickness of 15 μm of second layer coating in upper preparation.
The present embodiment is found by Muffle furnace high temperature aerobic environment certification test, in 1000 DEG C, under 30min, the present embodiment
In modification charcoal-aero gel it is higher by 32% than untreated charcoal-aero gel antioxygenic property.
Embodiment 2
1. by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder powder, the ball milling 5h in ball mill cross 300 meshes, so
It is afterwards Si:C:Al according to several powder quality ratios2O3=65%:20%:15% is uniformly mixed, and uniform powder is fallen in graphite
Crucible embeds charcoal-aero gel fritter, and 1400 DEG C of high-temperature process 30min in argon atmosphere prepare with a thickness of 45 μ
The first layer coating of m.
2. flow 100g/h, using argon gas as carrier gas, hydrogen and argon gas are carrier gas using trichloromethyl silane as raw material
The flow of body, hydrogen and argon gas is respectively 1.5m3/ h and 1m3/ h brings trichloromethyl silane into reaction chamber by bubbling mode
In, in chemical vapor deposition stove at 1100 DEG C, 20h is deposited, i.e., on the basis of the first layer coating of charcoal-aero gel surface preparation
The charcoal-aero gel (modified charcoal-aero gel) with gradient antioxidant coating is made with a thickness of 25 μm of second layer coating in upper preparation.
The present embodiment is found by Muffle furnace high temperature aerobic environment certification test, in 1000 DEG C, under 30min, the present embodiment
In modification charcoal-aero gel it is higher by 35% than untreated charcoal-aero gel antioxygenic property.
Embodiment 3
1. by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder, B2O3Powder powder, the ball milling 5h in ball mill cross 300
Then mesh is Si:C:Al according to several powder quality ratios2O3: B2O3=60%:20%:15%:5% is uniformly mixed, will be equal
Even powder falls in graphite crucible, charcoal-aero gel fritter is embedded, 1400 DEG C of high-temperature process 30min in argon atmosphere,
Prepare the first layer coating with a thickness of 45 μm.
2. flow 100g/h, using argon gas as carrier gas, hydrogen and argon gas are carrier gas using trichloromethyl silane as raw material
The flow of body, hydrogen and argon gas is respectively 1.5m3/ h and 1m3/ h brings trichloromethyl silane into reaction chamber by bubbling mode
In, in chemical vapor deposition stove at 1100 DEG C, 20h is deposited, i.e., on the basis of the first layer coating of charcoal-aero gel surface preparation
Charcoal-aero gel (the Modified Activated Carbon with gradient antioxidant coating is made with a thickness of 25 μm of second layer coating (SiC coating) in upper preparation
Aeroge).
The present embodiment is found by Muffle furnace high temperature aerobic environment certification test, in 1000 DEG C, under 30min, the present embodiment
In modification charcoal-aero gel it is higher by 36% than untreated charcoal-aero gel antioxygenic property.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 2, the difference is that:
Step 1. in, by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder powder, the ball milling 5h in ball mill, mistake
Then 300 meshes are Si:C:Al according to several powder quality ratios2O3=65%:20%:15% is uniformly mixed, by uniform powder
Material falls in graphite crucible, charcoal-aero gel fritter is embedded, 1000 DEG C of high-temperature process 60min, preparation obtain in argon atmosphere
Obtain first layer coating.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 2, the difference is that:
Step 1. in, by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder powder, the ball milling 5h in ball mill, mistake
Then 300 meshes are Si:C:Al according to several powder quality ratios2O3=65%:20%:15% is uniformly mixed, by uniform powder
Material falls in graphite crucible, charcoal-aero gel fritter is embedded, 1800 DEG C of high-temperature process 20min, preparation obtain in argon atmosphere
Obtain first layer coating.
Comparative example 1
Using untreated charcoal-aero gel, the examination examination of Muffle furnace high temperature aerobic environment is carried out at 1000 DEG C, under 30min
It tests, it is as shown in table 1 to obtain its oxidative mass loss.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that: do not include step 2..
Comparative example 3
Comparative example 3 is substantially the same manner as Example 3, the difference is that: do not include step 1., directly in the table of charcoal-aero gel
Wheat flour is for SiC coating.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 1, the difference is that:
Step 1. in, by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder, SiO2Powder, B2O3Powder powder, in ball milling
Ball milling 6h in machine crosses 300 meshes, is then Si:C:Al according to several powder quality ratios2O3: SiO2: B2O3=50%:20%:
15%:8%:7% is uniformly mixed, and uniform powder is fallen in graphite crucible, charcoal-aero gel fritter is embedded, in argon gas gas
1300 DEG C of high-temperature process 30min in atmosphere, prepare first layer coating.
Comparative example 5
Comparative example 5 is substantially the same manner as Example 2, the difference is that:
Step 1. in, by high-purity (>=99.5%) Si powder, C powder, Al2O3Powder powder, the ball milling 5h in ball mill, mistake
Then 300 meshes are Si:C:Al according to several powder quality ratios2O3=50%:25%:25% is uniformly mixed, by uniform powder
Material falls in graphite crucible, charcoal-aero gel fritter is embedded, 1400 DEG C of high-temperature process 30min, preparation obtain in argon atmosphere
Obtain first layer coating.
As can be known from the results of Table 1, when only when the surface of charcoal-aero gel prepares first layer coating, oxidative mass loss is
50%, 15% is improved only than untreated charcoal-aero gel antioxygenic property, when the surface only in charcoal-aero gel prepares the second layer
Coating (when SiC coating), oxidative mass loss 42% improve only 23% than untreated charcoal-aero gel antioxygenic property,
And it is anti-oxidant compared to untreated charcoal-aero gel for the modification charcoal-aero gel produced by the present invention with gradient antioxidant coating
Performance improves 30% or more, is that the collective effect of the first layer coating and second layer coating significantly improves in the present invention
The excellent modification charcoal-aero gel of antioxygenic property has been made in the antioxygenic property of charcoal-aero gel.It is independent on the surface of charcoal-aero gel
Prepare first layer coating or second layer coating improve charcoal-aero gel antioxygenic property it is unconspicuous the reason is that, although system of the present invention
Standby first layer coating can effectively avoid micron-sized mixed powder enter the charcoal-aero gel internal nanostructure in and
It can be improved the antioxygenic property of charcoal-aero gel to a certain extent, but its antioxygenic property needs the second layer coating to increase
By force；And SiC coating is directlyed adopt although on the surface of charcoal-aero gel, the antioxygenic property of charcoal-aero gel can be improved, but can existed
Two problems: 1, surface covering consistency is limited, and oxygen is easy to enter inside charcoal-aero gel by coating microdefect, causes
Oxidation；2, simple SiC coating can be also deep into inside charcoal-aero gel, and density is caused to increase, certain hole inside charcoal-aero gel
Structure can be filled by SiC, be destroyed；Second layer coating is directly individually thus prepared on the surface of charcoal-aero gel, charcoal-aero gel
Antioxygenic property promoted it is unobvious.
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 method for improving charcoal-aero gel antioxygenic property, which is characterized in that described method includes following steps:
(1) charcoal-aero gel embed using mixed powder and carry out high-temperature process under inert atmosphere protection, in the charcoal gas
The surface of gel prepares first layer coating, the mixed powder include silicon powder 55~85% by percentage to the quality, carbon dust 5~
25% and alumina powder 5~20%, the partial size of the silicon powder, the carbon dust and the alumina powder is 300~500 mesh；With
It (2) is carrier gas and using hydrogen and argon gas as diluent gas, passing through using argon gas using trichloromethyl silane as reaction gas
It learns vapour deposition process and prepares the second layer coating on the basis of first layer coating prepared by step (1), thus in the charcoal
The surface of aeroge is made by the first layer coating and the coat composed gradient antioxidant coating of the second layer to improve charcoal
The antioxygenic property of aeroge.
2. according to the method described in claim 1, it is characterized by:
The mixed powder also includes the silicon dioxide powder that mass percent is 0~5%, and the partial size of the silicon dioxide powder is 300
~500 mesh.
3. method according to claim 1 or 2, it is characterised in that:
The mixed powder also includes the boron oxide powder that mass percent is 0~5%, and the partial size of the boron oxide powder is 300~500
Mesh.
4. according to the method described in claim 3, it is characterized by:
The mixed powder is by silicon powder 55~85%, carbon dust 5~20% and alumina powder 5~15%, two by percentage to the quality
Silica powder 0~5% and boron oxide powder 0~5% form.
5. according to the method described in claim 1, it is characterized by:
The inert atmosphere is argon atmosphere or nitrogen atmosphere.
6. according to the method described in claim 1, it is characterized by:
The temperature of the high-temperature process is 1300~1600 DEG C, and the time of the high-temperature process is 30~60min.
7. according to the method described in claim 1, it is characterized by:
The second layer is prepared on the basis of by chemical vapour deposition technique in the first layer coating prepared by step (1) to apply
During layer, the flow of the trichloromethyl silane is 60~200g/h, and the flow of the hydrogen is 0.2~1.5m3/ h,
And/or the flow of the argon gas is 0.5~2m3/h。
8. according to the method described in claim 1, it is characterized by:
In step (2), the temperature of chemical vapor deposition is 950~1100 DEG C, and the time of chemical vapor deposition is 20~100h.
9. according to the method described in claim 1, it is characterized by:
In step (2), trichloromethyl silane is brought into chemical vapor deposition stove to pass through chemical gaseous phase by bubbling mode
Sedimentation prepares the second layer coating on the basis of first layer coating prepared by step (1).
10. the modified charcoal-aero gel as made from the described in any item methods of claim 1 to 9, which is characterized in that the Modified Activated Carbon
Aeroge includes the gradient antioxidant coating of charcoal-aero gel with the surface for being formed in the charcoal-aero gel.
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| CN201910438900.7A CN110115961A (en) | 2019-05-24 | 2019-05-24 | A kind of method improving charcoal-aero gel antioxygenic property and thus obtained modified charcoal-aero gel |
| CN201910711840.1A CN110237783B (en) | 2019-05-24 | 2019-08-02 | Method for improving oxidation resistance of carbon aerogel and modified carbon aerogel prepared by method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115110311A (en) * | 2022-07-08 | 2022-09-27 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method of high-temperature-resistant alumina aerogel felt and alumina aerogel felt |
| CN115160026A (en) * | 2022-07-12 | 2022-10-11 | 西北工业大学 | Preparation method of heat-insulating wave-absorbing foam material |
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| FI122230B (en) * | 2009-07-02 | 2011-10-31 | Aalto Korkeakoulusaeaetioe | Fluid repellent material |
| US8629076B2 (en) * | 2010-01-27 | 2014-01-14 | Lawrence Livermore National Security, Llc | High surface area silicon carbide-coated carbon aerogel |
| CN102503581B (en) * | 2011-09-22 | 2013-04-24 | 中南大学 | Long-term high-temperature oxidation-resistant multi-element composite ceramic coating for carbon/carbon composite material and preparation and application methods thereof |
| CN104311143B (en) * | 2014-10-14 | 2016-03-30 | 中国人民解放军国防科学技术大学 | A kind of method improving carbon aerogel composite material antioxidant property |
| CN104446656B (en) * | 2014-12-15 | 2016-10-05 | 航天特种材料及工艺技术研究所 | A kind of preparation method of porous carbon materials ORC |
| CN107473761B (en) * | 2016-06-08 | 2020-07-07 | 中国科学院金属研究所 | Heat-proof and load-bearing integrated carbon aerogel/ceramic layered composite material and preparation method and application thereof |
| CN109179373B (en) * | 2018-11-29 | 2020-09-01 | 航天特种材料及工艺技术研究所 | Antioxidant carbon aerogel material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115110311A (en) * | 2022-07-08 | 2022-09-27 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method of high-temperature-resistant alumina aerogel felt and alumina aerogel felt |
| CN115110311B (en) * | 2022-07-08 | 2024-01-12 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method of high-temperature-resistant alumina aerogel felt and alumina aerogel felt |
| CN115160026A (en) * | 2022-07-12 | 2022-10-11 | 西北工业大学 | Preparation method of heat-insulating wave-absorbing foam material |
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