CN104250107A - Method for in-situ synthesis of Si3N4 coating on carbon foam surface - Google Patents
Method for in-situ synthesis of Si3N4 coating on carbon foam surface Download PDFInfo
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- CN104250107A CN104250107A CN201310495482.8A CN201310495482A CN104250107A CN 104250107 A CN104250107 A CN 104250107A CN 201310495482 A CN201310495482 A CN 201310495482A CN 104250107 A CN104250107 A CN 104250107A
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Abstract
Belonging to the technical field of new materials, the invention relates to a method for in-situ synthesis of an Si3N4 coating on a carbon foam surface. The method includes the steps of: (1) taking phenolic resin as the basic raw material, and conducting atmospheric physical foaming to obtain a phenolic foam substrate with uniform air holes; (2) using tetraethyl orthosilicate as the main raw material, utilizing hydrolysis under acidic conditions to obtain a required sol solution; (3) subjecting the phenolic foam substrate of step (1) to ultrasonic cleaning and drying, then immersing the substrate into the sol solution of step (2), and dipping coating under ultrasonic vibration conditions to obtain a sol coating sample; and (4) placing the sol coating sample of step (3) into an atmosphere hot pressing furnace, conducting thermal insulation for 4h in a nitrogen atmosphere at 1400DEG C, and carrying out sintering, thus obtaining the sample of Si3N4 coating in-situ synthesized on the carbon foam surface.
Description
Technical field
The present invention relates to a kind of at foam carbon material surface in situ synthesis Si
3n
4the method of coating, belongs to new material technology field.
Background technology
Foam carbon material is as a kind of novel charcoal material, and unique pore space structure gives the superior performance such as its low density, high strength, conduction, heat conduction, thermally-stabilised, chemically stable, is widely used in the fields such as aerospace, metallurgy, chemical industry, environmental protection, electronics.But the weakness of oxidizable corrosion in high temperature oxidative atmosphere, has a strong impact on the performance of foam carbon material excellent properties, and then restrict its application in various fields.Therefore, need a kind of effective antioxidant defense method badly, under the prerequisite not affecting foam carbon material structure and performance, stop the oxidation of foam carbon material.
At present, the antioxidant defense of foam carbon material mainly comprises matrix modification and coating two kinds, and coating is the most effective antioxidant defense measure.Si
3n
4because of the mechanics of its uniqueness, optics, electrical properties and desirable passivation, antioxidant property, be also a kind of important coating and thin-film material.Though prior art relates to Si
3n
4research in the oxidation resistant coating of Carbon Materials, but be mostly for matrix of carbon/carbon composite materials surface and carry out being compounded to form certain compound coating with SiC etc., and the anti-oxidant Si of foam carbon material for porous
3n
4coating yet there are no correlation technique report.
The present invention is based on Si
3n
4the gas-solid mechanism formed, propose a kind of technique simple, be easy to control, the sol impregnation that low temperature easily adulterates prepares Si in conjunction with high-temperature ammonolysis process
3n
4the novel method of coating, improves the antioxidant property of foam carbon material greatly, for its large-scale development in fields such as aerospace, chemical industry, electronics, environmental protection and application provide certain theoretical basis and laboratory reference.
Summary of the invention
Main purpose of the present invention is to provide a kind of at foam carbon material surface in situ synthesis Si
3n
4the method of coating.
The present invention adopts tetraethoxy to be main raw material, through the hydrolysis of acidic conditions and the sol solution of the still aging acquisition viscous consistency of normal temperature; Then the phenol formaldehyde foam of normal pressure physical blowing gained is immersed above-mentioned sol solution, to phenol formaldehyde foam matrix coating under ultrasonic oscillation condition; Finally fully dry coating sample is placed in atmosphere hot pressing furnace, is incubated 4h reaction in nitrogen atmosphere at 1400 DEG C and burns till.
The present invention is a kind of at foam carbon material surface in situ synthesis Si
3n
4the method of coating, its advantage is that technique is simple, and easy handling, cost is low, and coating density is high, and antioxidant effect is good.
Concrete step of preparation process and principle as follows:
(1) appropriate heat-reactive phenolic resin is taken, sodium bicarbonate, tween 80, tosic acid is added successively under strong magnetic agitation condition, three's adding proportion is respectively 5wt%, 6wt% and 20wt% of resol quality, strong magnetic agitation mixed for several minutes, several minutes are dried under mixture being placed in about 80 DEG C, baking oven, foamed solidification, obtains phenol formaldehyde foam matrix.
(2) tetraethoxy and the dehydrated alcohol of appropriate volume ratio is measured respectively, at room temperature strong magnetic agitation mixing.In this mixture, add the deionized water of appropriate volume, and adjust the pH value of mixed solution with 10% nitric acid, strong magnetic agitation certain hour.Finally, add the sucrose solution of certain volume to said mixture, strong magnetic agitation a few hours, at room temperature still aging a couple of days, obtain required sol solution.
(3) by the phenol formaldehyde foam matrix ultrasonic cleaning of step (1), after oven dry, immerse in the sol solution of step (2), under ultrasonic oscillation condition, flood certain hour surface obtain coating.After the abundant drying of each coating, carry out Dipping next time, repeatedly flood for several times, obtain collosol coating sample.
(4) the collosol coating sample of step (3) is placed in atmosphere hot pressing furnace, under certain temperature, in nitrogen atmosphere, insulation a few hours reaction, obtains Carbon foam surface in situ synthesis Si
3n
4coating sample.For reduce that collosol coating and phenol formaldehyde foam matrix thermal expansion coefficient difference cause peel off, the generation of the defect such as tiny crack, warming machine is made as: first with the ramp of 10 DEG C/min to 300 DEG C, then with the ramp of 5 DEG C/min to 500 DEG C, last with the ramp to 1400 DEG C of 2 DEG C/min, insulation 4h, naturally cool to room temperature, obtained oxidation resistant coating Carbon foam sample.
Accompanying drawing explanation
Fig. 1 foam carbon material surface in situ synthesis of the present invention Si
3n
4the process flow sheet of coating;
Fig. 2 embodiment one gained Si
3n
4coating XRD figure is composed;
Fig. 3 embodiment one gained Si
3n
4coating SEM photo;
Fig. 4 embodiment one gained Si
3n
4coating transverse section SEM photo;
Embodiment
Embodiment one:
(1) 10g heat-reactive phenolic resin is taken, sodium bicarbonate, tween 80, tosic acid is added successively under strong magnetic agitation condition, three's adding proportion is respectively 5wt%, 6wt% and 20wt% of resol quality, strong magnetic agitation mixing 3 ~ 5min, mixture is placed in oven dry 5 ~ 10min under about 80 DEG C, baking oven, foamed solidification, obtains phenol formaldehyde foam matrix.
(2) tetraethoxy that volume ratio is 10:3 and dehydrated alcohol is measured respectively, at room temperature strong magnetic agitation mixing.In this mixture, add the deionized water that volume ratio is tetraethoxy 33vol%, and be 3.5 by the pH value of 10% nitric acid adjustment mixed solution, strong magnetic agitation 30min.Finally, add to said mixture the sucrose solution that volume ratio is tetraethoxy 27vol%, strong magnetic agitation 4h, at room temperature still aging 72h, obtain required sol solution.
(3), by the phenol formaldehyde foam matrix ultrasonic cleaning of step (1), after oven dry, immerse in the sol solution of step (2), Dipping 20min under hyperacoustic condition.After the abundant drying of each coating, carry out Dipping next time, repeatedly flood for several times, obtain being coated with the collosol coating sample that hierachy number is followed successively by 1,2,3.
(4) the collosol coating sample of the different coating number of times of step (3) is placed in atmosphere hot pressing furnace, at 1400 DEG C, in nitrogen atmosphere, insulation 4h reaction, obtains Carbon foam surface in situ synthesis Si
3n
4the sample of coating.For reduce that collosol coating and phenol formaldehyde foam matrix thermal expansion coefficient difference cause peel off, the generation of the defect such as tiny crack, warming machine is made as: first with the ramp of 10 DEG C/min to 300 DEG C, then with the ramp of 5 DEG C/min to 500 DEG C, last with the ramp to 1400 DEG C of 2 DEG C/min, insulation 4h, naturally cool to room temperature, obtained oxidation resistant coating Carbon foam sample.
Claims (4)
1. a Carbon foam surface in situ synthesis Si
3n
4the method of coating, is characterized in that: described preparation method comprises following steps,
(1) preparation of phenol formaldehyde foam matrix
Take appropriate heat-reactive phenolic resin, sodium bicarbonate, tween 80, tosic acid is added successively under strong magnetic agitation condition, three's adding proportion is respectively 5wt%, 6wt% and 20wt% of resol quality, strong stirring mixed for several minutes, several minutes are dried under mixture being placed in about 80 DEG C, baking oven, foamed solidification, obtains phenol formaldehyde foam matrix.
(2) preparation of sol solution
Measure tetraethoxy and the dehydrated alcohol of appropriate volume ratio respectively, at room temperature strong magnetic agitation mixing.In this mixture, add the deionized water of appropriate volume, and adjust the pH value of mixed solution with 10% nitric acid, strong magnetic agitation certain hour.Finally, add certain volume sucrose solution to said mixture, strong magnetic agitation a few hours, at room temperature still aging a couple of days, obtain required sol solution.
(3) preparation of collosol coating sample
By the phenol formaldehyde foam matrix ultrasonic cleaning of step (1), dry, immerse in the sol solution of step (2), under ultrasonic oscillation condition, flood certain hour surface obtain coating.After the abundant drying of each coating, carry out Dipping next time, repeatedly flood for several times, obtain collosol coating sample.
(4) preparation of oxidation resistant coating Carbon foam
The collosol coating sample of step (3) is placed in atmosphere hot pressing furnace, and under certain temperature, in nitrogen atmosphere, insulation a few hours reaction, obtains oxidation resistant coating sample.For reduce that collosol coating and phenol formaldehyde foam matrix thermal expansion coefficient difference cause peel off, the generation of the defect such as tiny crack, warming machine is made as: first with the ramp of 10 DEG C/min to 300 DEG C, then with the ramp of 5 DEG C/min to 500 DEG C, last with the ramp to 1400 DEG C of 2 DEG C/min, insulation 4h, naturally cool to room temperature, obtained oxidation resistant coating Carbon foam sample.
2. the one according to claims 1 is at foam carbon material surface in situ synthesis Si
3n
4the method of coating, is characterized in that: collosol coating matrix is phenol formaldehyde foam matrix, to ensure the physical compatibility of colloidal sol and matrix.
3. the one according to claims 1 is at foam carbon material surface in situ synthesis Si
3n
4the method of coating, is characterized in that: under acidic conditions, tetraethoxy is hydrolyzed, and forms uniform properties sol solution, floods, reach the even coating of coating to phenol formaldehyde foam matrix under ultrasonic oscillation condition.
4. the one according to claims 1 is at foam carbon material surface in situ synthesis Si
3n
4the method of coating, is characterized in that: 1400 DEG C, and in nitrogen atmosphere, the nitrogenize that the charing of phenol formaldehyde foam matrix and teos hydrolysis generate SiO is carried out simultaneously, decreases Carbon foam and Si
3n
4the stripping of coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495482.8A CN104250107B (en) | 2013-06-28 | 2013-10-22 | A kind of Carbon foam surface in situ synthesizes Si3N4The method of coating |
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| CN201310265163.8 | 2013-06-28 | ||
| CN201310265163 | 2013-06-28 | ||
| CN2013102651638 | 2013-06-28 | ||
| CN201310495482.8A CN104250107B (en) | 2013-06-28 | 2013-10-22 | A kind of Carbon foam surface in situ synthesizes Si3N4The method of coating |
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| Publication Number | Publication Date |
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| CN104250107A true CN104250107A (en) | 2014-12-31 |
| CN104250107B CN104250107B (en) | 2017-12-08 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658598A (en) * | 2018-05-15 | 2018-10-16 | 潘荣强 | A kind of preparation method of Carbon foam |
| CN114604870A (en) * | 2022-02-24 | 2022-06-10 | 南京智汇环境气象产业研究院有限公司 | Method for preparing foam carbon material from wood block |
Citations (5)
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|---|---|---|---|---|
| JPH01286979A (en) * | 1988-05-12 | 1989-11-17 | Toshiba Ceramics Co Ltd | Carbonaceous composite material |
| CN1887940A (en) * | 2006-06-26 | 2007-01-03 | 北京航空航天大学 | Carbon-base brake material for track vehicle |
| CN102515851A (en) * | 2011-12-26 | 2012-06-27 | 天津大学 | Preparation method for silicon-nitride-based coating on surface of porous ceramic |
| CN103011836A (en) * | 2012-12-03 | 2013-04-03 | 北京中材人工晶体研究院有限公司 | Carbon material surface coat composition and preparation method of coat |
| CN103030135A (en) * | 2013-01-05 | 2013-04-10 | 航天材料及工艺研究所 | Preparation method of antioxidant high-heat-conductivity foamy carbon material |
-
2013
- 2013-10-22 CN CN201310495482.8A patent/CN104250107B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01286979A (en) * | 1988-05-12 | 1989-11-17 | Toshiba Ceramics Co Ltd | Carbonaceous composite material |
| CN1887940A (en) * | 2006-06-26 | 2007-01-03 | 北京航空航天大学 | Carbon-base brake material for track vehicle |
| CN102515851A (en) * | 2011-12-26 | 2012-06-27 | 天津大学 | Preparation method for silicon-nitride-based coating on surface of porous ceramic |
| CN103011836A (en) * | 2012-12-03 | 2013-04-03 | 北京中材人工晶体研究院有限公司 | Carbon material surface coat composition and preparation method of coat |
| CN103030135A (en) * | 2013-01-05 | 2013-04-10 | 航天材料及工艺研究所 | Preparation method of antioxidant high-heat-conductivity foamy carbon material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658598A (en) * | 2018-05-15 | 2018-10-16 | 潘荣强 | A kind of preparation method of Carbon foam |
| CN114604870A (en) * | 2022-02-24 | 2022-06-10 | 南京智汇环境气象产业研究院有限公司 | Method for preparing foam carbon material from wood block |
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| CN104250107B (en) | 2017-12-08 |
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