CN101905979A - Method for preparing carbon/carbon-silicon carbide (C/C-SiC) composite self-sealing and anti-oxidation coating - Google Patents
Method for preparing carbon/carbon-silicon carbide (C/C-SiC) composite self-sealing and anti-oxidation coating Download PDFInfo
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- CN101905979A CN101905979A CN2009100721945A CN200910072194A CN101905979A CN 101905979 A CN101905979 A CN 101905979A CN 2009100721945 A CN2009100721945 A CN 2009100721945A CN 200910072194 A CN200910072194 A CN 200910072194A CN 101905979 A CN101905979 A CN 101905979A
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Abstract
The invention discloses an effective method for preparing a C/C-SiC composite self-sealing and anti-oxidation coating by conversion of a precursor, which belongs to the field of carbon material protection. A Si3N4/SiC/B4C anti-oxidation coating with a certain self-sealing capability is prepared by taking active group-containing polysilazane precursor polymer as a raw material and adding a proper amount of B4C packing and by a coating-sintering process. The process comprises the following steps of: firstly, mixing polysilazane and the B4C powder in a certain proportion uniformly to prepare slurry, and coating the slurry on the surface of a C/C-SiC composite subjected to surface treatment; secondly, placing the C/C-SiC composite in a nitrogen furnace to perform crosslinking and curing at the temperature of between 200 and 300 DEG C for 1 to 2h; thirdly, heating at a speed of 5 DEG C/min till the temperature is 1,200 to 1,300 DEG C, keeping the temperature for 1 to 2h and then slowly cooling to room temperature; and finally, performing reinforcement treatment for 1 to 2 times to obtain the Si3N4/SiC/B4C ceramic anti-oxidation coating with a uniform and compact surface. The method has the advantages of low preparation temperature, controllable product ingredient and structure, high performance and the like, has obvious advantages in aspects of crack closure, preparation cost reduction and the like and is an anti-oxidation coating preparation method with a great prospect.
Description
Technical field
The present invention relates to C/C-SiC composite material surface Si
3N
4/ SiC/B
4The preparation method of C gradient, self-healing anti-oxidation coating belongs to raw material of wood-charcoal material protection field.
Background technology
Carbon/silicon carbide double-basis matrix material (C/C-SiC) occurs as thermal structure material as far back as the eighties in 20th century, be a kind of be to strengthen body with the carbon fiber, with carbon, silicon carbide is the matrix material of matrix, combine carbon fiber and strengthen superior mechanical property and good chemistry and the thermostability of ceramic matrix of body, have characteristics such as good wear resisting property and high-strength light, main at present as brake material, as the brake facing of space shuttle, the brake material of bullet train and sedan limousine.But, make the physicals and the rapid deterioration of mechanical property of material because the C/C-SiC matrix material just begins to take place oxidizing reaction when temperature is higher than 400 ℃ in oxygen atmosphere is arranged.With C/C-SiC composite airplane carbon/carbon brake disc is example, and when oxidative mass loss reached 10%, braking efficiency will be affected, even causes brake to be lost efficacy, and then can not guarantee the safety of aircraft brake.Therefore for improving the use temperature of C/C-SiC matrix material in aerobic environment, enlarge its range of application and field, research and development C/C-SiC matrix material antioxygen coating technology becomes an important topic of people's concern in recent years.
The preparation method who is used for raw material of wood-charcoal material high-temperature oxidation resistant coating at present has entrapping method, chemical Vapor deposition process (CVD) method, sol-gel method, plasma spraying method etc.:
(1) entrapping method.This method is that test specimen is placed liquid state or solid state medium, realizes diffusion reaction, finally forms coating on the test specimen surface.Mainly based on solid diffusion, generally with Pure Silicon Metal and SiC etc. as bleed, under the Ar gas shiled, in 1600～2000 ℃ of scopes, material is carried out the high temperature solid state diffusion and handles.The treatment temp of this method is higher relatively, and the homogeneity that obtains coating is relatively poor.
(2) chemical Vapor deposition process (CVD).This method is by gaseous substance chemical reaction to take place under certain conditions, makes the solid phase of generation deposit the method for preparing coating on matrix.Utilize the coating kind of CVD method preparation to mainly contain SiC, Si at present
3N
4, BN, TiC etc., its shortcoming is that cost is higher, working efficiency is lower.
(3) plasma spraying method.This method is to utilize arc plasma gun to produce 8000～15000 ℃ high temperature, with any material that does not decompose or distil when melting, by defeated people's device, is being sprayed on after the high-temperature fusion on the solid substrates surface.It can spray TiC, SiC, B
3C, WC, Al
2O
3Etc. types of coatings.But this method is had relatively high expectations to appointed condition, and production cost is higher, and produces bigger residual thermal stress easily between coating and matrix, influences the use properties of coating.
(4) sol-gel method.This is that employing ester compound and metal alkoxide are a kind of chemical process that raw material prepares solid inorganic material, its specific practice is that matrices of composite material is soaked in people's colloidal sol, reintroducing liquid level separates in water in air, then through super-dry, be sintered to substrate surface, generally will repeatedly be hydrolyzed-the exsiccant process just can reach requirement.This method requirement coated material can be wetting with base material, and its viscosity and flowability are had certain requirement.
At the problem that exists in the aforesaid method, the present invention adopts Stainless Steel via Precursor Pyrolysis gradient, self-healing anti-oxidation coating.The preceramic polymer polysilazane that employing contains active group is a raw material, adds B
4The C filler, by coating-sintering process, the Si that preparation has certain self-healing ability
3N
4/ SiC/B
4The C coating.Advantages such as this method has not only that technological temperature is lower, the composition of product and controllable structure, performance are good, and have remarkable advantages making crackle up and reduce aspect such as cost of manufacture, be the oxidation resistant coating method that has development prospect.
Summary of the invention
The effective preparation method who the purpose of this invention is to provide a kind of C/C-SiC matrix material self-healing anti-oxidation coating.Polysilazane is that people are contained silicon by a kind of novel high polymer material of chemical process synthetic on the main chain in recent years, and it cracking takes place in certain temperature range is converted into SiC/Si
3N
4Pottery, aspects such as the vapour pressure of the rate of permeation of oxygen, material, thermal expansivity, hardness, bonding force all are the most effective coated materials at present when high temperature.In preparation process, polysilazane can be penetrated into matrix inside, is forming gradient cladding at the interface; Added B
4The C filler has been filled up the volumetric shrinkage of precursor in cracking process on the one hand, simultaneously B
4C and O
2React, generate B
2O
3Glass state material, healed cracks effectively improves the self-healing ability of coating.
C/C-SiC composite material surface Si
3N
4/ SiC/B
4The preparation technology of C oxidation resistant coating is:
(1) surface treatment of C/C-SiC matrix material: with surface grinding, the polishing of C/C-SiC matrix material, after washing, used the dehydrated alcohol ultrasonic cleaning again 20 minutes, oven dry is stand-by then.
(2) preparation of coated material: with molecular weight is that polysilazane and the particle diameter of 2000-3000 is the B of 1～2 μ m
4The C powder is that 50～60%: 40～50% mixed becomes uniform slurry by mass ratio.
(3) brushing-sintering process: the slurry that (2) are made is coated with evenly to be smeared on the C/C-SiC composite material surface of handling through (1), then sample is put into nitrogen furnace.Heat-processed is: at first 200～300 ℃ of crosslinking curings 1～2 hour, be warming up to 1200～1300 ℃ with 5 ℃/minute speed again, be incubated 1～2 hour, be cooled to room temperature with 5 ℃/minute speed then, obtain Si
3N
4/ SiC/B
4C oxidation-resistant ceramic coating.
(4) enhancement process: take out the sample after handle (3), the slurry that adopts (2) to make is brushed once more, puts into nitrogen furnace then, carries out sintering once more by the temperature schedule of (3).Carry out enhancement process repeatedly 1～2 time.Coating preparation is finished after above-mentioned steps.
Described C/C-SiC composite coating is characterized in that: described coating is by Si
3N
4, SiC, B
4Three kinds of phase composites of C, and it is comparatively even to distribute.
Described C/C-SiC composite coating is characterized in that: described coating has strong self-healing function.B in the coating
4The C filler has been filled up the volumetric shrinkage of precursor in cracking process on the one hand, generates B simultaneously in oxidising process
2O
3Glass state material, healed cracks effectively.
Described C/C-SiC composite coating is characterized in that: described coating is a gradient cladding.Alleviate interfacial stress because polysilazane is penetrated into the inner gradient cladding that forms of matrix, improved the bonding strength between coating and matrix.
Described C/C-SiC composite coating preparation method is characterized in that: the oxidation resistant coating that can be used for preparing other raw material of wood-charcoal material such as graphite, C/C, C/SiC.
Advantage of the present invention is:
(1), overcome other method material therefor and C/C-SiC matrix material mother metal thermal expansivity differs bigger shortcoming because the brush material that is coated with of the present invention can form the relative approaching coating of thermal expansivity with the C/C-SiC matrix material.
(2) in preparation process, polysilazane can be penetrated into matrix inside, is forming gradient cladding at the interface, improves the bonding strength between coating and matrix, and alleviates interfacial stress.
(3) added B
4The C filler has been filled up the volumetric shrinkage of precursor in cracking process on the one hand, generates B simultaneously in oxidising process
2O
3Glass state material, healed cracks has effectively improved the self-healing ability of coating.
(4) equipment that this method adopted is simple, and preparation temperature is lower, and the composition of product and controllable structure are easy to implement.Being the perfect method that a kind of low cost, high benefit prepare raw material of wood-charcoal material oxidation resistant coating, also is one of oxidation resistant coating method that has development prospect.
Description of drawings
Accompanying drawing 1 is a C/C-SiC matrix material oxidation resistant coating surface topography stereoscan photograph.As can be seen from Figure, the coatingsurface behind the sintering is more smooth, even compact, defectives such as flawless.
Accompanying drawing 2 is C/C-SiC matrix material oxidation resistant coating cross section scanned photograph and element distribution curve.As can be seen from the figure, partial coating material and matrix form mechanical snap, and the line sweep spectrum curve of elements such as B, C, Si all is being skewed at the interface simultaneously, and the phenomenon that has the element mutual diffusion between coating and the matrix is described.Elemental diffusion can be alleviated the stress that matrix and coating produce owing to thermal expansivity does not match at the interface, thereby improves the bonding force between matrix and the coating.
Accompanying drawing 3 is coated material XRD figure spectrums through 1300 ℃ of sintering after products under nitrogen environment.As can be seen from Figure, on the XRD figure spectrum B is arranged
4C, SiC and Si
3N
4Diffraction peak.
Embodiment
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing.
The preparation method of the oxidation resistant coating of embodiment 1:C/C-SiC matrix material
(1) surface treatment of C/C-SiC matrix material: with surface grinding, the polishing of C/C-SiC matrix material, after washing, used the dehydrated alcohol ultrasonic cleaning again 20 minutes, oven dry is stand-by then.
(2) preparation of coated material: with molecular weight is that polysilazane and the particle diameter of 2000-3000 is the B of 1～2 μ m
4The C powder is that 60%: 40% mixed becomes uniform slurry by mass ratio.
(3) brushing-sintering process: the slurry that above-mentioned (2) are made is applied on the C/C-SiC composite material surface after (1) processing, put into nitrogen furnace, heat-processed is: crosslinking curing 1 hour in the time of 200 ℃ at first, be warming up to 1250 ℃ with 5 ℃ of/minute clock rate again, be incubated 1 hour, be cooled to room temperature with 5 ℃ of/minute clock rate then.
(4) enhancement process: take out the C/C-SiC matrix material after handle (3), the slurry that adopts (2) to make is brushed once more, puts into nitrogen furnace then, carries out sintering once more by the temperature schedule of (3).Carry out enhancement process repeatedly 2 times.Coating preparation is finished after above-mentioned steps.
This coating is in 900 ℃ well-oxygenated environment, and rear oxidation weightlessness was-0.3wt% in 72 hours.
The preparation method of the oxidation resistant coating of embodiment 2:C/C-SiC matrix material
(1) surface treatment of C/C-SiC matrix material: with surface grinding, the polishing of C/C-SiC matrix material, after washing, used the dehydrated alcohol ultrasonic cleaning again 20 minutes, oven dry is stand-by then.
(2) preparation of coated material: with molecular weight is that polysilazane and the particle diameter of 2000-3000 is the B of 1～2 μ m
4The C powder is that 50%: 50% mixed becomes uniform slurry by mass ratio.
(3) sintering process: the slurry that above-mentioned (2) are made is applied on the C/C-SiC composite material surface after (1) processing, put into nitrogen furnace, heat-processed is: crosslinking curing 1 hour in the time of 250 ℃ at first, be warming up to 1200 ℃ with 5 ℃ of/minute clock rate again, be incubated 2 hours, be cooled to room temperature with 5 ℃ of/minute clock rate then.
(4) enhancement process: take out the C/C-SiC double-basis matrix material after handle (3), the slurry that adopts (2) to make is brushed once more, puts into nitrogen furnace then, and the temperature parameter of pressing (3) carries out sintering once more.Coating preparation is finished after above-mentioned steps.Carry out enhancement process repeatedly 2 times.
This coating is in 900 ℃ well-oxygenated environment, and rear oxidation weightlessness was 0.5wt% in 72 hours.
The preparation method of the oxidation resistant coating of embodiment 3:C/C-SiC matrix material
(1) surface treatment of C/C-SiC matrix material: with surface grinding, the polishing of C/C-SiC matrix material, after washing, used the dehydrated alcohol ultrasonic cleaning again 20 minutes, oven dry is stand-by then.
(2) preparation of coated material: with molecular weight is that polysilazane and the particle diameter of 2000-3000 is the B of 1～2 μ m
4The C powder is that 60%: 40% mixed becomes uniform slurry by mass ratio.
(3) sintering process: the slurry that above-mentioned (2) are made is applied on the C/C-SiC composite material surface after (1) processing, put into nitrogen furnace, heat-processed is: crosslinking curing 2 hours in the time of 200 ℃ at first, be warming up to 1300 ℃ with 5 ℃ of/minute clock rate again, be incubated 1 hour, be cooled to room temperature with 5 ℃ of/minute clock rate then.
(4) enhancement process: take out the C/C-SiC double-basis matrix material after handle (3), the slurry that adopts (2) to make is brushed once more, puts into nitrogen furnace then, and the temperature parameter of pressing (3) carries out sintering once more.Carry out enhancement process repeatedly 2 times.Coating preparation is finished after above-mentioned steps.
This coating is in 900 ℃ well-oxygenated environment, and rear oxidation weightlessness was 0.6wt% in 72 hours.
Claims (4)
1. a precursor transforms the method for preparing C/C-SiC matrix material self-healing anti-oxidation coating.Realize by following steps:
(1) selection of precursor: it is the polysilazane of 2000-3000 that precursor is selected molecular weight for use, is colourless liquid under the room temperature.
(2) surface treatment of C/C-SiC matrix material: with surface grinding, the polishing of C/C-SiC matrix material, after washing, used the dehydrated alcohol ultrasonic cleaning again 20 minutes, oven dry is stand-by then.
(3) preparation of coated material: with polysilazane and particle diameter is the B of 1～2 μ m
4The C powder is that 50～60%: 40～50% mixed becomes uniform slurry by mass ratio.
(4) brushing-sintering process: the slurry that above-mentioned (3) are made evenly is applied on the C/C-SiC composite material surface after (2) processing, put into nitrogen furnace, heat-processed is: crosslinking curing 1～2 hour in the time of 200～300 ℃ at first, be warming up to 1200～1300 ℃ with 5 ℃ of/minute clock rate again, be incubated 1～2 hour, be cooled to room temperature with 5 ℃ of/minute clock rate then, obtain Si
3N
4/ SiC/B
4C oxidation-resistant ceramic coating.
(5) enhancement process: take out the sample after handle (4), the slurry that adopts (3) to make is brushed once more, puts into nitrogen furnace then, carries out sintering once more by the temperature schedule of (4).Carry out enhancement process repeatedly 1～2 time.Coating preparation is finished after above-mentioned steps.
2. the preparation method of C/C-SiC matrix material oxidation resistant coating according to claim 1 is characterized in that: described being coated with in the brush material, polysilazane ceramic yield after cracking is 82%, and split product is Si
3N
4/ SiC pottery.
3. the preparation method of C/C-SiC matrix material oxidation resistant coating according to claim 1 is characterized in that: described coating is by Si
3N
4, SiC, B
4Three kinds of phase composites of C, and it is comparatively even to distribute.Coating has strong self-healing function.
4. the preparation method of C/C-SiC matrix material oxidation resistant coating according to claim 1 is characterized in that: this method can be used for preparing the oxidation resistant coating of other raw material of wood-charcoal material such as graphite, C/C, C/SiC.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515870A (en) * | 2011-12-10 | 2012-06-27 | 西北工业大学 | Preparation method of C/SiC-ZrB2-ZrC ultrahigh-temperature ceramic-based composite material |
| CN103727357A (en) * | 2013-09-11 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Ultrathin high-temperature-resistant thermal insulation material structure |
| CN105622119A (en) * | 2015-12-31 | 2016-06-01 | 中物功能材料研究院有限公司 | Ceramic-based composite coating and preparation method thereof |
| CN112845494A (en) * | 2020-12-04 | 2021-05-28 | 南京斯博伏特新材料有限公司 | Method for preparing sewage treatment material by utilizing agricultural waste |
| CN113563113A (en) * | 2021-08-09 | 2021-10-29 | 重庆国际复合材料股份有限公司 | High-temperature oxidation-resistant coating on surface of carbon-based composite material and preparation method thereof |
-
2009
- 2009-06-04 CN CN2009100721945A patent/CN101905979A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515870A (en) * | 2011-12-10 | 2012-06-27 | 西北工业大学 | Preparation method of C/SiC-ZrB2-ZrC ultrahigh-temperature ceramic-based composite material |
| CN102515870B (en) * | 2011-12-10 | 2013-04-17 | 西北工业大学 | Preparation method of C/SiC-ZrB2-ZrC ultrahigh-temperature ceramic-based composite material |
| CN103727357A (en) * | 2013-09-11 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Ultrathin high-temperature-resistant thermal insulation material structure |
| CN105622119A (en) * | 2015-12-31 | 2016-06-01 | 中物功能材料研究院有限公司 | Ceramic-based composite coating and preparation method thereof |
| CN112845494A (en) * | 2020-12-04 | 2021-05-28 | 南京斯博伏特新材料有限公司 | Method for preparing sewage treatment material by utilizing agricultural waste |
| CN113563113A (en) * | 2021-08-09 | 2021-10-29 | 重庆国际复合材料股份有限公司 | High-temperature oxidation-resistant coating on surface of carbon-based composite material and preparation method thereof |
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Application publication date: 20101208 |