CN108727059A - It is a kind of can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics - Google Patents
It is a kind of can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics Download PDFInfo
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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Abstract
The invention discloses a kind of can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, this method is by Polycarbosilane and containing the silane of vinyl, pass through Polycarbosilane of the hydrosilylation synthesis with heat curable properties, then using organic foam as template, dipping obtains the organic foam precast body containing heat cure property Polycarbosilane, the foam preform is heat-treated again, realize the crosslinking curing of the removing and Polycarbosilane of solvent, high temperature pyrolysis is finally carried out, foam silicon carbide ceramics are obtained.The preparation method is simple, and cost is relatively low, and the SiC foam ceramics linear shrinkage ratio prepared is less than 3%, the small 0.6g/cm of bulk density3, between 75%~91%, flexural strength can use open pore rate up to 2.0~2.5MPa in 1100 DEG C of long-times.
Description
Technical field
The invention belongs to ceramic foam technical fields, and in particular to a kind of to prepare silicon carbide bubble can be thermally cured Polycarbosilane
The preparation method of foam ceramics.
Background technology
Foam silicon carbide ceramics have good characteristic：Adaptability is good, anti-oxidant, corrosion-resistant, coefficient of thermal expansion is low, thermostabilization
Property is good, pyroconductivity is low, permeability is high, fluid absorption is good, selective penetrated property is high, energy absorption or damping are good, Yi Jiying
The small equal excellent properties of power load deformation.It is widely used in the necks such as filtering, bioceramic, sound-absorbing, catalyst carrier and chemical filler
Domain.In recent years, the demand with people to foamed ceramics was growing, and preparing high-performance foam ceramics also becomes the task of top priority.
Since SiC is a kind of strong covalent bond compound, self-diffusion coefficient is very small, and direct sintering temperature connects 2000 DEG C, leads to
All be addition sintering aid in the case of often reduce its sintering temperature (She Jihong, the development of the bright silicon carbide ceramics in the east of a river with answer
With ceramic engineerings, 1998,32 (3):3‐11).
In numerous preparation methods, Foam dipping method has a clear superiority：It is fine by organic foam unique three
The slurry prepared is uniformly coated in organic foam mesh skeleton structure and forms foam preform by open mesh skeleton,
Drying process keeps the slurry on foam framework muscle more secured, then burns up Organic Foam Material without pressure, and it is similar to obtain a kind of structure
The foamed ceramics of foaming structure.The technological operation is simple, is readily produced, and the ceramics that stomata connectivity is good and porosity is high can be made
Product.
(Yao Xiumin, Huang Zhengren, Tan Shou flood Polycarbosilane low-temperature sintering silicon carbide nets in traditional Foam dipping method
Development [J] Journal of Inorganic Materials of eye porous ceramics, 2010,25 (02):168‐172.；Liu Wei, Liyang, Chen Lu Polycarbosilanes
Low temperature preparation foam silicon carbide ceramics [J] silicate journals, 2011,39 (11):1763‐1767.；Chen Lu, Liyang, Liu Wei are poly-
Preparation [J] modern mechanicals of carbon silane low-temperature sintering foam silicon carbide ceramics, 2011 (06):60‐61+87.；Sun Wen flies low temperature
Prepare foam silicon carbide ceramics and its performance study [D] Guizhou University, 2017.), mostly use based on Silicon Carbide Powder
Ingredient and binder and solvent is wanted to prepare slurry, using organic foam as template, dipping obtains precast body, is finally sintered precast body and obtains
To foam silicon carbide ceramics.After the addition of sintering aid, sintering prepares SiC foam ceramics temperature mostly at 1400 DEG C or more.Beam
(Liang Hanqin, Yao Xiumin, Huang Zhengren, Liu Xue build liquid phase generating process [J] mechanic when silicon carbide ceramics liquid-phase sinterings to Chinese qin
Journey material, 2015,39 (02):34-37.) SiC foam ceramic sintering temperature and sintering mechanism are studied, SiC foam pottery
Porcelain is mainly that glass is generated with respect to the cladding of SiC particulate, connection function and cenotype mullite.(Liu Wei, Liyang, Chen Lu are poly- by Liu Wei
Carbon silane low temperature preparation foam silicon carbide ceramics [J] silicate journals, 2011,39 (11):1763-1767.) use organic mould
Plate infusion process bonds SiC micro mists for cracking with Polycarbosilane in 1000 DEG C and is prepared for SiC foam ceramics in an inert atmosphere,
Foamed ceramics linear shrinkage ratio is larger, and flexural strength is increased with the increase of solid concentration, first increases with the increase of PCS contents and drops again
It is low；Solid concentration is 69.6%, and when Polycarbosilane content is 10%, bending strength is up to 3.9MPa.Liu Jian (Liu Jian, Xu Yunshu,
Xiong Liangping, Xu Guangliang low pressure molding low-temperature sintering SiC porous ceramics [J] of SiC powder containing presoma China powder technology,
2009,15(03):Polycarbosilane and SiC powder 28-30.) is used to prepare the porous potteries of SiC for raw material low pressure molding low-temperature sintering
Porcelain has studied influence of the Polycarbosilane content to SiC porous ceramics performances.Sem analysis shows that Polycarbosilane pyrolysis product will
SiC particulate bonds, and porous ceramics has interconnected open-celled structure.
In conclusion in traditional Foam dipping method, slurry mainly with Silicon Carbide Powder particle be mainly at
Point, in sintering process, binder forms connection between Silicon Carbide Powder particle, has certain mechanical property to be formed
The ceramic foam of energy.Binder can be divided into：Electrodeless metal oxide and organic compound Polycarbosilane, the former is to foamed ceramics
Element composition has larger impact, and sintering preparation temperature is high, at 1300 DEG C or more；The latter can foam in sintering process, and content is low
When, bond effect unobvious, when content is high, the holding of intensity and hole to foam adversely affects, and foamed ceramics line is received
Shrinkage is larger, and in preparing slurry process, no matter the dispersion between that binder and silicon carbide powder is problem, cannot be very
The slurry of stable homogeneous is formed well, this has detrimental effect to the performance of final foamed ceramics.
Therefore, in 105272266 A of patent CN, Li Siwei only uses Polycarbosilane as the precursor of foamed ceramics, with
Solvent xylene prepares slurry, using processed polyurethane foam as template, hanging product is made, first passes through in convection oven
Reason, then foam silicon carbide ceramics are sintered to obtain in high temperature furnace.But in the processing procedure in convection oven, especially for big
Size, when the larger hanging product of volume is handled, oxidation homogeneity is similarly difficult to ensure：It will appear local too high oxygen level；Very
Polycarbosilane to internal layer is not fully developed crosslinking curing, in sintering process, can cause the change of foam caved in hole
Shape.The key point that limitation polymer-derived method prepares foam silicon carbide ceramics is the crosslinking curing process of Polycarbosilane.
Invention content
Present situation in view of the above technology, the present invention is intended to provide a kind of preparation of the low-cost high-efficiency of foam silicon carbide ceramics
Method.
Developing itself has the Polycarbosilane of heat cure property, during precursor method prepares foam silicon carbide ceramics
It no longer needs to carry out cure treatment.With the pioneer that the Polycarbosilane with heat curable properties is unique foam silicon carbide ceramics
Body prepares dipping solution by solvent of dimethylbenzene, using organic foam as template, prepares the foam preform containing dipping solution,
By further high-temperature process, complete solvent removing and Polycarbosilane it is self-curing, it is no longer necessary to air does not melt technique,
Ensure do not occur phenomena such as ceramics itself foam, flow, caving in into silicon carbide ceramics transition process in Polycarbosilane simultaneously, protects
The hole and structural property of foam silicon carbide ceramics are demonstrate,proved, this technique preparation flow is simple, sufficient raw, has prodigious
Actual application value.
In order to achieve the above technical purposes, as shown in Figure 1, the present invention is with Polycarbosilane (PCS) and containing the silane of vinyl
Reaction, makes vinyl group be introduced into PCS structures, obtains the novel Polycarbosilane (PVCS) containing vinyl.Due to the PVCS
Structure in contain two kinds of active groups of-C=C- and Si-H, to assign its own thermally cross-linkable characteristic.Then, leaching is prepared
Stain solution, is impregnated by template of organic foam.Then, the organic foam precast body obtained to dipping is heat-treated, complete
At the removing of solvent and the self-crosslinking solidification of Polycarbosilane.Finally the foam after solidification is pyrolyzed, is had in the process
Machine silicon foam decomposes completely, noresidue, and foaming and serious volume contraction will not occur for the Polycarbosilane after solidification, to control
The pore structure and intensity of foam obtain the SiC foam ceramics of function admirable.
That is, the technical scheme is that：It is a kind of can be thermally cured the preparation that Polycarbosilane prepares foam silicon carbide ceramics
Method includes the following steps：
(1) it is made in structure comprising-C=C- and Si-H active groups with containing the silane reaction of vinyl with Polycarbosilane
Group, and be dissolvable in water organic solvent can be thermally cured Polycarbosilane, can be thermally cured Polycarbosilane as presoma；
(2) Polycarbosilane dissolving will be can be thermally cured and prepares dipping solution, and using organic foam as template, complete the leaching of foam
Stain obtains the organic foam precast body containing dipping solution；
(3) organic foam precast body is heat-treated in an inert atmosphere, realizes solvent removal and Polycarbosilane itself
Crosslinking curing；
(4) high temperature pyrolysis is carried out to the organic foam after crosslinking curing, obtains foam silicon carbide ceramics.
The PCS is to reset the Polycarbosilane synthesized by polydimethylsiloxane cracking, and softening point is 200~240 DEG C,
Number-average molecular weight is 1600~1950.
Preferably, being free of Cl elements in the silane containing vinyl.
Preferably, containing multiple vinyl in the silane containing vinyl, such as contain 4-C=C- bases
Group.
Preferably, in the silane containing vinyl, on silicon atom other than connecting vinyl group, it is also connected with it
The saturated alkanes such as his organic group, such as connection methyl, ethyl or propyl.
The silane containing vinyl is unlimited, including tetravinyl cyclotetrasiloxane, three (isoolefine propoxyl group) ethylene
Base silane.
In the step (1), as a kind of realization method, detailed process is as follows：
It is 1 by mass ratio:0.1~1 Polycarbosilane is placed in the silane containing vinyl in reaction vessel, is added first
Organic solvent is uniformly miscible, adds Si-H addition reaction catalysts, after vacuumizing displacement high-purity argon gas, is protected in high-purity argon gas
Under, under normal pressure, heating carries out Si-H addition reactions, and the first organic solvent and unreacted silane chemical combination are removed after being cooled to room temperature
Object is contained the heat cure Polycarbosilane of-C=C- and Si-H active groups.
First organic solvent is unlimited, and first organic solvent includes one kind in dimethylbenzene, toluene, acetone
Or it is a variety of.Preferably, the volume mass ratio of first organic solvent and presoma is 5ml/g~50ml/g；
Preferably, the mass ratio of the Polycarbosilane and the silane containing vinyl is 1:(0.1~0.9)；
The Si-H addition reaction catalysts include chloroplatinic acid；
Preferably, the volume mass ratio of the Si-H addition reaction catalysts and presoma is 10ppm~400ppm；
Preferably, react under normal pressure, it is heated to 90~100 DEG C under high-purity argon gas protection, and insulation reaction 6h~
Stop reaction after 30h, reaction mixture is placed in rotary evaporator, 60~100 DEG C are evaporated under reduced pressure out solvent and unreacted silane
Compound obtains the Polycarbosilane containing vinyl.
In the step (1), the computational methods of Si-H addition reaction degree are：Measure before reaction with react after mixture
Infrared spectrum finds out 2100cm on each comfortable infrared spectrum respectively-1(Si-H) and 1250cm-1(Si-CH3) at characteristic absorption peak
The ratio between absorbance ISiH/ISiH4, that is, (I before reactingSiH/ISiH4) with react after ISiH/ISiH4), the Si-H extents of reaction are found out as the following formula,
PSiH：
In the step (2), as a kind of realization method, detailed process is as follows：It is mixed with PVCS and the second organic solvent
It is made into slurry, using organic foam as template, dipping arrives organic foam precast body；
Preferably, the solution concentration is 30~80%wt；
Preferably, the vacuum degree is 0.1Pa~1Pa；
Preferably, the organic foam is unlimited, including polyurethane foam, polystyrene foam etc.；
Second organic solvent is one or more in tetrahydrofuran, acetone, n-hexane, toluene and dimethylbenzene.
In the step (3), as a kind of realization method, detailed process is as follows：By organic foam precast body in indifferent gas
In atmosphere, 200 DEG C~400 DEG C are warming up to the heating rate of 1 DEG C/min~15 DEG C/min, keeps the temperature 1h~8h.
In the step (4), as a kind of realization method, detailed process is as follows：By step (3), treated, and precast body exists
In inert atmosphere, with the heating rate of 5 DEG C/min~50 DEG C/min, 1000 DEG C~1200 DEG C are heated to, heat preservation 0.5h~3h is small
When, it then cools to room temperature.Obtain foam silicon carbide ceramics.
Preferably, the bulk density 0.5g/cm of the SiC foam ceramics3, open pore rate between 80%~91% it
Between, flexural strength reaches 2.3MPa.
One kind preparing foam silicon carbide ceramics can be thermally cured Polycarbosilane, is made using the above method.
(1) present invention makes vinyl group be introduced into PCS structures with Polycarbosilane (PCS) with containing the silane reaction of vinyl
In, obtain the novel Polycarbosilane with heat cure property.Dipping solution is prepared, is impregnated by template of organic foam.It connects
It, the organic foam precast body obtained to dipping is heat-treated, and the self-crosslinking of the removing and Polycarbosilane of completing solvent is solid
Change.Finally the foam preform after solidification is sintered, silicon foams decompose completely in the process, noresidue, solidification
Foaming and serious volume contraction will not occur for Polycarbosilane afterwards, to control the pore structure and intensity of foam, obtaining property
SiC foam that can be excellent is ceramic.Bulk density<0.6g/cm3, between 80%~91%, flexural strength reaches open pore rate
More than 2.0MPa.
(2) present invention improves polymer-derived method and prepares foam silicon carbide ceramics, and the sic foam homogeneity of preparation is stablized, no
Air not melting process is needed, valuable scheme is provided to prepare large scale foamed ceramics for polymer-derived method.
(3) present invention is impregnated using solution, and in the foam preform of preparation, Polycarbosilane is uniform, dipping effect higher.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of foam silicon carbide ceramics of the present invention.
Specific implementation mode
With reference to embodiment, present invention is further described in detail, it should be pointed out that embodiment described below purport
Convenient for the understanding of the present invention, and any restriction effect is not played to it.
Embodiment 1：
With can be thermally cured Polycarbosilane prepare foam silicon carbide ceramics preparation method it is as follows：
(1) preparation of PVCS
The Polycarbosilane synthesized is reset by polydimethylsiloxane cracking, softening point is 230 DEG C, and number-average molecular weight is
1750。
The PCS and tetravinyl cyclotetrasiloxane are pressed 1:0.3 mass ratio is added in reaction kettle, is by dimethylbenzene/PCS
The ratio addition dimethylbenzene of 10ml/g is uniformly miscible, then chloroplatinic acid is added as catalysis using the ratio that chloroplatinic acid/PCS is 100ppm
Agent after vacuumizing displacement high-purity argon gas, is then heated to 120 DEG C, stops reaction after insulation reaction 20h, will be produced after being cooled to room temperature
Object solution is placed in distilling apparatus, under high-purity argon gas protection, is warming up to 80 DEG C, is evaporated under reduced pressure out solvent and unreacted silicon alkanisation
Object is closed, product PVCS is obtained.
The silicon hydrogen extent of reaction that PCS is obtained using the computational methods of the Si-H addition reaction degree is 18%.Product
PVCS both contains vinyl, also contains Si-H, and dissolubility is excellent.
(2) dipping obtains organic foam precast body
With PVCS obtained above and dimethylbenzene mixing wiring solution-forming, viscosity 20Pas；Using organic foam as template,
Pressure is 0.5Pa, is impregnated, and after dipping, squeezes out redundant solution and obtains organic foam precast body.
(3) it is heat-treated organic foam precast body
Organic foam precast body is put into stove, after vacuumizing displacement high-purity argon gas three times, by organic foam in high-purity argon
In gas atmosphere, 220 DEG C are warming up to the heating rate of 10 DEG C/min, keeps the temperature 1h.
(4) pyrolysis prepares foam silicon carbide ceramics
In argon gas atmosphere, by step (3) treated precast body with the heating rate of 5 DEG C/min, 1100 DEG C are heated to,
Heat preservation 1h hours, then cools to room temperature, obtains black bright foam silicon carbide ceramics.Bulk density 0.5g/cm3, open pore
Between rate 83%, flexural strength reaches 2.3MPa.
Using EMGA-620W model oxygen-nitrogen analyzers, the oxygen content for measuring foam silicon carbide ceramics obtained above is
8.6wt%.
Embodiment 2：
With can be thermally cured Polycarbosilane prepare foam silicon carbide ceramics preparation method it is as follows：
The Polycarbosilane synthesized is reset by polydimethylsiloxane cracking, softening point is 220 DEG C, and number-average molecular weight is
1700。
The PCS and three (isoolefine propoxyl group) vinyl silanes are pressed 1:0.5 mass ratio is added in reaction kettle, by diformazan
The ratio addition dimethylbenzene that benzene/PCS is 15ml/g is uniformly miscible, then chlorine platinum is added with the ratio that chloroplatinic acid/PCS is 100ppm
Acid is vacuumized as catalyst, after replacing high-purity argon gas three times, is then heated to 120 DEG C, is stopped after insulation reaction 22h anti-
It answers, reaction mixture is placed in distilling apparatus after being cooled to room temperature, under high-purity argon gas protection, be warming up to 90 DEG C, be evaporated under reduced pressure out
Solvent and unreacted silicon hydride compounds, obtain product PVCS.
The silicon hydrogen extent of reaction that PCS is obtained using the computational methods of the Si-H addition reaction degree is 15%, product
PVCS both contains vinyl, also contains Si-H, and dissolubility is excellent.
(2) dipping obtains organic foam precast body
With PVCS obtained above and dimethylbenzene mixing wiring solution-forming, viscosity 30Pas；Using organic foam as template,
It completes to impregnate under 0.1Pa pressure, after dipping, squeezes out redundant solution and obtain organic foam precast body.
(3) it is heat-treated organic foam precast body
Organic foam precast body is put into stove, is vacuumized, after replacing high-purity argon gas three times, by organic foam in high-purity argon
In gas atmosphere, 200 DEG C are warming up to the heating rate of 6 DEG C/min, keeps the temperature 3h.
(4) pyrolysis prepares foam silicon carbide ceramics
In high-purity argon gas, by step (3), treated that organic foam precast body is warming up to 1000 DEG C with 10 DEG C/min,
5h is kept the temperature, then cools to room temperature, obtains black bright foam silicon carbide ceramics.Bulk density 0.4g/cm3, open pore rate
Between 84%, flexural strength reaches 2.1MPa.
Using EMGA-620W model oxygen-nitrogen analyzers, the oxygen content for measuring foam silicon carbide ceramics obtained above is
6.1wt%.
Embodiment 3：
With can be thermally cured Polycarbosilane prepare foam silicon carbide ceramics preparation method it is as follows：
The preparation of step (1) PVCS is the same as embodiment 1
(2) dipping obtains organic foam precast body
With PVCS obtained above and dimethylbenzene mixing wiring solution-forming, viscosity 40Pas；Using organic foam as template,
Organic foam precast body is obtained after dipping.
Step (3) and (four) are the same as embodiment 2
Obtain black bright foam silicon carbide ceramics.Bulk density 0.5g/cm3, between open pore rate 85%, flexural strength
Up to 2.3MPa.
Using EMGA-620W model oxygen-nitrogen analyzers, the oxygen content for measuring foam silicon carbide ceramics obtained above is
7.5wt%.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. it is a kind of can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, it is characterized in that：Including walking as follows
Suddenly：
(1) with Polycarbosilane with containing the silane reaction of vinyl, be made in structure comprising-C=C- and Si-H active groups,
And be dissolvable in water organic solvent can be thermally cured Polycarbosilane, can be thermally cured Polycarbosilane as presoma；
(2) Polycarbosilane dissolving will be can be thermally cured and prepares dipping solution, and using organic foam as template, completed the dipping of foam, obtain
To the organic foam precast body containing dipping solution；
(3) organic foam precast body is heat-treated in an inert atmosphere, realizes the friendship of solvent removal and Polycarbosilane itself
Connection solidification；
(4) high temperature pyrolysis is carried out to the organic foam after crosslinking curing, obtains foam silicon carbide ceramics.
2. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：Polycarbosilane described in step 1 is to be reset to synthesize by polydimethylsiloxane cracking, and softening point is 200~240 DEG C, number
Average molecular weight is 1600~1950.
3. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：The silane containing vinyl described in step 1 includes tetravinyl cyclotetrasiloxane and three (isoolefine propoxyl group) vinyl
At least one of both silane.
4. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：In the step (1), detailed process is as follows：
It is 1 by mass ratio:0.1~1 Polycarbosilane is placed in the silane containing vinyl in reaction vessel, and it is organic to be added first
Solvent is uniformly miscible, adds Si-H addition reaction catalysts, after vacuumizing displacement high-purity argon gas, under high-purity argon gas protection,
Under normal pressure, heating carries out Si-H addition reactions, and the first organic solvent and unreacted silane compound are removed after being cooled to room temperature,
Contained the heat cure Polycarbosilane of-C=C- and Si-H active groups.
5. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：First organic solvent includes one or more in dimethylbenzene, toluene, acetone；
Preferably, the volume mass ratio of first organic solvent and presoma is 5ml/g~50ml/g；
Preferably, the mass ratio of the presoma and the silane containing vinyl is 1:(0.1~0.9)；
The Si-H addition reaction catalysts include chloroplatinic acid；
Preferably, the volume mass ratio of the Si-H addition reaction catalysts and presoma is 10ppm~400ppm；
Preferably, being reacted under normal pressure, 90~150 DEG C are heated under high-purity argon gas protection, and stop after insulation reaction 6h~30h
It only reacts, reaction mixture is placed in rotary evaporator, 60~100 DEG C are evaporated under reduced pressure out solvent and unreacted silicon hydride compounds,
Contained the Polycarbosilane of-C=C- and Si-H active groups.
6. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：In the step (2), detailed process is as follows：
It is made into dipping solution with heat cure Polycarbosilane and the mixing of the second organic solvent, completes organic foam under vacuum
Dipping, obtains the organic foam precast body containing dipping solution.
7. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：A concentration of 30~80%wt of the dipping solution；
Preferably, the vacuum degree is 0.1Pa~1Pa；
Preferably, the organic foam is polyurethane foam；
Second organic solvent is one or more in tetrahydrofuran, acetone, n-hexane, toluene and dimethylbenzene.
8. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：In the step (3), detailed process is as follows：
In an inert atmosphere by organic foam, 200 DEG C~400 DEG C are warming up to the heating rate of 1 DEG C/min~15 DEG C/min, protected
Warm 1h~8h；Si―H addition reaction occurs for two kinds of active groups of-C=C- and Si-H in heat cure Polycarbosilane, completes intermolecular
There is " crosslinking curing of Polycarbosilane itself " that is, in step 3 in crosslinking.
9. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：In the step (4), detailed process is as follows：
Under an inert atmosphere by step (3) treated foam preform, with the heating rate of 5 DEG C/min~50 DEG C/min, add
Heat keeps the temperature 0.5h~3h hours, then cools to room temperature to 1000 DEG C~1200 DEG C；Polycarbosilane after crosslinking curing occurs to divide
Solution deviates from organic molecule, obtains silicon carbide ceramics.
10. as described in claim 1 can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics, feature
It is：The oxygen content of foam silicon carbide ceramics obtained is in 5~10wt%；
Preferably, the bulk density 0.5g/cm of foam silicon carbide ceramics obtained3, open pore rate between 80%~91% it
Between, flexural strength reaches 2.3MPa.
Preferably, in an inert atmosphere, 1100 DEG C, after 100h, flexural strength retention rate is 90% or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204730A (en) * | 2019-05-22 | 2019-09-06 | 中国科学院宁波材料技术与工程研究所 | A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof |
| CN110563955A (en) * | 2019-10-24 | 2019-12-13 | 中国科学院宁波材料技术与工程研究所 | Liquid curable metal-based polycarbosilane and preparation method thereof |
| CN112126064A (en) * | 2020-09-24 | 2020-12-25 | 长沙科航特种织造有限公司 | Preparation method of novel solid silicon carbide ceramic precursor |
| CN113896539A (en) * | 2021-11-02 | 2022-01-07 | 航天材料及工艺研究所 | High-temperature-resistant oxidation-resistant light heat-insulating foam material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4631179A (en) * | 1985-05-28 | 1986-12-23 | Ethyl Corporation | Process for the production of silicon carbide by the pyrolysis of a polycarbosilane polymer |
| CN105085925A (en) * | 2015-09-28 | 2015-11-25 | 中国人民解放军国防科学技术大学 | Synthesis method of polycarbosilane capable of being used for thermosetting crosslinking |
| CN105272266A (en) * | 2015-11-27 | 2016-01-27 | 厦门大学 | Preparation method of precursor converted silicon carbide foam ceramics |
| CN107337468A (en) * | 2016-12-23 | 2017-11-10 | 辽宁卓异新材料有限公司 | A kind of preparation method and application of foamed ceramics porous burner medium |
-
2018
- 2018-07-09 CN CN201810747263.7A patent/CN108727059A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4631179A (en) * | 1985-05-28 | 1986-12-23 | Ethyl Corporation | Process for the production of silicon carbide by the pyrolysis of a polycarbosilane polymer |
| CN105085925A (en) * | 2015-09-28 | 2015-11-25 | 中国人民解放军国防科学技术大学 | Synthesis method of polycarbosilane capable of being used for thermosetting crosslinking |
| CN105272266A (en) * | 2015-11-27 | 2016-01-27 | 厦门大学 | Preparation method of precursor converted silicon carbide foam ceramics |
| CN107337468A (en) * | 2016-12-23 | 2017-11-10 | 辽宁卓异新材料有限公司 | A kind of preparation method and application of foamed ceramics porous burner medium |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204730A (en) * | 2019-05-22 | 2019-09-06 | 中国科学院宁波材料技术与工程研究所 | A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof |
| CN110204730B (en) * | 2019-05-22 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Polycarbosilane containing high-activity crosslinkable group and preparation method thereof |
| CN110563955A (en) * | 2019-10-24 | 2019-12-13 | 中国科学院宁波材料技术与工程研究所 | Liquid curable metal-based polycarbosilane and preparation method thereof |
| CN112126064A (en) * | 2020-09-24 | 2020-12-25 | 长沙科航特种织造有限公司 | Preparation method of novel solid silicon carbide ceramic precursor |
| CN113896539A (en) * | 2021-11-02 | 2022-01-07 | 航天材料及工艺研究所 | High-temperature-resistant oxidation-resistant light heat-insulating foam material and preparation method thereof |
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