CN102503581B - Long-term high-temperature oxidation-resistant multi-element composite ceramic coating for carbon/carbon composite material and preparation and application methods thereof - Google Patents

Long-term high-temperature oxidation-resistant multi-element composite ceramic coating for carbon/carbon composite material and preparation and application methods thereof Download PDF

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CN102503581B
CN102503581B CN 201110283692 CN201110283692A CN102503581B CN 102503581 B CN102503581 B CN 102503581B CN 201110283692 CN201110283692 CN 201110283692 CN 201110283692 A CN201110283692 A CN 201110283692A CN 102503581 B CN102503581 B CN 102503581B
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熊翔
曾毅
张武装
殷玲
郭顺
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Central South University
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Abstract

The invention provides a long-term high-temperature oxidation-resistant multi-element composite ceramic coating for a carbon/carbon composite material and preparation and application methods thereof. The long-term high-temperature oxidation-resistant multi-element composite ceramic coating is a composite coating on the surface of the carbon/carbon composite material and sequentially (from inside to outside) comprises a SiC connection layer prepared with an embedding method, a SiC sealing layer prepared with a chemical vapor deposition method and a SiO2-Y2Si2O7-ZrSiO4-Al2SiO5 ceramic layer prepared with a brush coating method and an in-situ oxidation reaction method, wherein the SiC connection layer is combined with a matrix and exerts the function of connecting the matrix, the SiC sealing layer exerts the function of filling defects of an inner layer, and the outermost SiO2-Y2Si2O7-ZrSiO4-Al2SiO5 ceramic layer serves as an oxygen blocking layer and exerts the function of self-healing and oxygen blocking. The long-term high-temperature oxidation-resistant multi-element composite ceramic coating has the advantages of firmness in combination with the matrix, no run-through crack, long-term high-temperature oxidation resistance, and capability of being completely applied to the preparation of non-direct-ablation heat-resistant structural members around the head and of the wings of a hypersonic aircraft and the preparation of a material for the tailpipe chamber of an aircraft engine.

Description

The polynary composite ceramic coat of the long-time high-temperature oxidation resistant of a kind of carbon/carbon composite and methods for making and using same
Technical field
The present invention relates to a kind of surface treatment of carbon/carbon composite, relate in particular to around a kind of head of hypersonic vehicle and the non-direct ablation heat resistant structure spare of wing with carbon/carbon composite and replace novel aeroengine thrust augmentation combustion chamber conventional high-temperature alloy material with the surperficial for a long time polynary composite ceramic coat of high-temperature oxidation resistant multilayer and the methods for making and using same thereof of carbon/carbon composite.
Background technology
Carbon/carbon composite is the new type high temperature material of carbon fiber reinforced carbon matrix body, and it is that U.S. Chance-Vought airline is serendipitous in 1958.Carbon/carbon composite is made of single carbon material fully, have high-strength modulus, density is low, thermal expansivity is little, anti-ablation, antifatigue, unreactiveness, dimensional stability are high, particularly the intensity temperature raises and the series of advantages such as rising and high-fracture toughness, low creep under the high temperature, be desirable thermal structure and ablation resistant material, be widely used in aerospace field.Especially be applied on the heat resistant structure spare of hypersonic vehicle, have the serial advantage of the heat-resisting grade of light weight.But easily oxidized when carbon/carbon composite uses, thereby cause its intensity decrease even complete failure in the high temperature aerobic environment.Under aerobic conditions, the initial oxidation temperature of carbon/carbon composite is 370 ℃; When being higher than 500 ℃, the rapid oxidation of carbon/carbon composite meeting, and catastrophic explosion occurs.And hypersonic vehicle is when high-speed flight, and its fuselage often will bear 1000 ℃-2200 ℃ temperature.For example the leading edge of a wing or the head high velocity air that will stand up to 2200 ℃ washes away, and the temperature up to 1000 ℃-1500 ℃ also will be born in all the other non-direct ablation positions of wing and fuselage.In addition, hypersonic vehicle also must be able to by long-time reusable requirement.Secondly, high temperature alloy is adopted in traditional aeroengine combustor buring chamber more, and the temperature out of combustion chamber has reached 1000 ℃-1500 ℃, and as with replacing alloy material with carbon/carbon composite, the weight of engine can alleviate greatly, and then the thrust-weight ratio of raising aircraft.Therefore, develop a kind of coating carbon/carbon composite of novel long-time high-temperature oxidation resistant, can be applied on the non-direct ablation parts of hypersonic vehicle wing and fuselage and on the combustion chamber of aircraft engine and have great significance.
Effective measure at the anti-oxidant composite ceramic coat of carbon/carbon composite surface-coated.The thermal expansivity of SiC and carbon base body are comparatively approaching, and good chemical compatibility is arranged.But single SiC coating has more defective (crackle and hole), is difficult to play the effect of long-time high-temperature oxidation resistant.Oxide ceramics can stop Sauerstoffatom to spread to carbon base body preferably, but can react with carbon base body under the high temperature.In addition, oxide ceramics often has higher thermal expansivity, and ceramic coating easily forms penetrating crack, and comparatively serious meeting comes off.Therefore, the of new generation ceramic composite coating of exploitation with good physics and chemistry consistency and good self-healing function has great importance.
Summary of the invention
Purpose of the present invention is exactly not mate the situation that causes being prone to defects i.e.cracks because of physics and chemistry for the carbon/carbon composite surface ceramic coat, design also prepares a kind of brand-new being combined with matrix firmly, without the function ceramics compound coating of the long-time resistance to high temperature oxidation of through-wall crack, and methods for making and using same.
The objective of the invention is to realize by following manner:
The preparation method of the polynary composite ceramic coat of the long-time high-temperature oxidation resistant of a kind of carbon/carbon composite,
It is from inside to outside successively preparation on the carbon/carbon composite surface: articulamentum, sealing ply and ceramic coating, described articulamentum is the SiC layer of entrapping method preparation, described sealing ply is the SiC layer of chemical Vapor deposition process preparation, and described ceramic coating is the SiO of spread coating and the preparation of in-situ oxidation reaction method 2-Y 2Si 2O 7-ZrSiO 4-Al 2SiO 5Ceramic layer.
It is with Si powder, Al that described entrapping method prepares articulamentum 2O 3Powder, C powder, SiC powder are raw material, and with the carbon/carbon composite embedding, high-temperature calcination gets final product behind the ball milling mixing, and the articulamentum thickness that obtains is about 30-50 μ m.
Concrete steps are as follows:
According to the quality proportioning be: Si 40-75%, Al 2O 32-13%, C 8-20%, SiC 10-38% take by weighing Si powder, Al 2O 3Powder, C powder, the SiC powder adds dispersion agent, takes out dry rear stand-by behind the abundant mixing of ball milling; At last, carbon/carbon composite is placed plumbago crucible, and with the powder of mixing it is buried fully, after crucible is put into High Temperature Furnaces Heating Apparatus, at 1700 ℃-2000 ℃ lower insulation 1.5-3h.Described Si powder, SiC powder, C powder, Al 2O 3Powder is preferred mistake 325 orders all.
Described chemical Vapor deposition process prepares sealing ply take trichloromethyl silane as SiC source, H 2Be carrier gas, Ar is diluent gas, at high temperature will be embedded with the carbon/carbon composite surface deposition SiC of articulamentum, and the sealing ply thickness that obtains is about 20-30 μ m.
Concrete steps are as follows:
Trichloromethyl silane is taken out of H from head tank with Bubbling method 2Mix in mixed gas tank with Ar, pass into again the chemical vapor deposition stove precursor reactant, after thermal degradation, after the residual gas filtration, taken away by vacuum pump; H 2/ trichloromethyl silane mol ratio=6-12, Ar flow are 150-280mlmin -1, deposition pressure<1kPa; Temperature is 800 ℃-1280 ℃, soaking time 3-12h.
Described spread coating and in-situ oxidation reaction method prepare SiO 2-Y 2Si 2O 7-ZrSiO 4-Al 2SiO 5Ceramic layer is with SiC powder, YAG powder and YSZ powder, mixes according to proportioning, adds the PVA solution preparation and becomes to brush slurry, then slurry is brushed equably on the carbon/carbon composite surface with articulamentum and sealing ply; High-temperature sample sintering after the brushing makes coating; At last, with its preoxidation in high temperature air, make ceramic coating by the in-situ oxidation reaction, the thickness of ceramic coating that obtains is about 50-70 μ m.
Concrete steps are as follows:
With SiC powder, YAG powder and YSZ powder according to quality 50-82: 15-30: the 3-20 proportioning is mixed, and adds the PVA solution preparation and becomes to brush slurry, and powder and PVA liquor capacity are than being 0.5-0.8; The PVA strength of solution is 2wt%-8wt%; Then slurry is brushed equably on the carbon/carbon composite surface with articulamentum and sealing ply; Sample oven dry after the brushing, high temperature sintering makes coating; At last, with its preoxidation 0.5-4h in 1300 ℃ of-1500 ℃ of air, make ceramic coating by the in-situ oxidation reaction.
The preparation of described YAG powder: with high-purity α-Al 2O 3Powder and Y 2O 3Powder take mol ratio as preparation in 5: 3, adopts planetary high-energy ball mill, as medium mixed powder is carried out wet-milling with dehydrated alcohol, and ratio of grinding media to material is 4-8, Ball-milling Time 20-36h.Ball milling makes yttrium aluminum garnet (YAG) powder after calcining 2-3h by 1400 ℃-1600 ℃.
Described YSZ powder is the partially stabilized ZrO of yttrium oxide 2Powder is the commercial powder of buying, and granularity is 10-40 μ m.
Above-mentioned slurry is brushed equably after having the carbon/carbon composite surface of articulamentum and sealing ply, and sample is dried 4h in 100 ℃ of constant temperature ovens.Dried sample is positioned in the vacuum carbon tube furnace, uses argon shield, and sintering 1-1.5h under 1300 ℃ of-1500 ℃ of temperature makes coating.
Polynary composite ceramic coat of the present invention is applied to prepare around the head of hypersonic vehicle and the non-direct ablation heat resistant structure spare of wing, and prepares the aeroengine thrust augmentation combustor material.
Method of the present invention can prepare the anti-oxidant function compound coating of the C/C matrix material of chemical vapor infiltration and/or the preparation of liquid impregnation technique.
Advantage and the positively effect of invention
Compared with prior art, advantage of the present invention and positively effect are embodied in:
(1) entrapping method prepares the effect of articulamentum.Because oxide ceramic coating has higher thermal expansivity and the problem bad with the chemical compatibility of carbon base body, easily causes the supercoat rapid failure.And the thermal expansivity of SiC and carbon base body comparatively approaches and chemical compatibility is better.Utilize SiC as internal layer, can effectively alleviate the thermal expansion mismatch between external coating (EC) and the matrix.In addition, utilizing entrapping method to prepare binder couse, to have technique simple, saves the advantage of cost.The most important thing is that this method can prepare the C-SiC coating with finite concentration gradient, can greatly alleviate the mismatch degree of CTE between coating and the C/C matrix material, make the coating sample have excellent thermal shock resistance.
(2) chemical Vapor deposition process prepares the effect of SiC intermediate seal layer.The ultimate principle of chemical vapour deposition is at a certain temperature, occurs between reactant to form coating at matrix surface behind the series of physical chemical transformation.The coating that the method is made is fine and close, purity is higher, and the tissue of coating, pattern, composition can be controlled.Utilize the defective of the standby SiC layer of this legal system in can well packing SiC articulamentum, and then sealing oxygen is to the passage of matrix rapid diffusion.
(3) spread coating and in-situ oxidation reaction method prepare SiO 2-Y 2Si 2O 7-ZrSiO 4-Al 2SiO 5The effect of ceramic coating.The advantage of spread coating be method simply, easily and fast, cost is low, can be easy to prepare the in advance coating system of design.Can improve chemistry and the physical compatibility of coating and generate serial silicate material by the in-situ oxidation reaction method.Amorphous carbon/silicon dioxide, pure aluminium silicate are given coating packing function, self-healing function and are hindered preferably the oxygen function; And high-melting-point and have preferably resistance to elevated temperatures and thermal shock resistance with yttrium silicate and zirconium silicate that SiC has an approximate thermal expansivity, thereby make a kind of chemistry of whole coating formation and physical compatibility good, resistant to elevated temperatures function compound coating.
(4) utilized the main advantage of above four kinds of methods to prepare with matrix and be combined firmly, without through-wall crack and Interlaminar Crack, had superior thermal shock resistance, can satisfy carbon/carbon composite and under well-oxygenated environment, use for a long time.
Description of drawings
The macro morphology of Fig. 1 coating that is the compound coating sample after different process is processed (is of a size of 20mm * 20mm * 5mm), from left to right be respectively: charcoal/Carbon Materials matrix, only has articulamentum sample of the present invention, have articulamentum of the present invention and sealing ply sample, have the sample of articulamentum of the present invention, sealing ply and ceramic coating.
Fig. 2 stereoscan photograph (a) outermost layer ceramic coating that is compound coating of the present invention before the reaction of carbon/carbon composite in-situ oxidation is surface topography (b) Cross Section Morphology that reacts of in-situ oxidation not, the A district represents articulamentum, the B district represents the intermediate seal floor, and the C district represents outermost layer YAG-SiC-YSZ ceramic coating without the in-situ oxidation responding layer.
Fig. 3 is compound coating carbon/carbon composite sample of the present invention compact surfaces pattern after the in-situ oxidation reaction;
Fig. 4 is compound coating carbon/carbon composite sample of the present invention coating specimen surface pattern behind stereoscan photograph (a) the oxidation 15h after the isothermal oxidation experiment; (b) coating specimen surface pattern behind the oxidation 150h; (c) coating sample Cross Section Morphology behind the oxidation 150h
Fig. 5 is the oxidation weight loss curve of compound coating sample of the present invention in 1500 ℃ of still airs.A is for having SiC/SiC/SiO 2-Y 2Si 2O 7-ZrSiO 4-Al 2SiO 5The oxidation curve of the carbon/carbon composite sample of composite ceramic coat; B is the oxidation curve with carbon/carbon composite sample of SiC/SiC coating.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
At first the C/C matrix material is cut into the block sample of 20 * 20 * 5mm, with using the fine grinding of 800# sand paper after the 400# sand papering chamfering, again with for subsequent use behind 120 ℃ of lower baking 1~2h after the alcohol wash;
What then carry out is that embedding treatment prepares the SiC articulamentum:
With Si powder, SiC powder, C powder, Al 2O 3Powder is the mixed powder that raw material prepares embedding.The powder quality proportioning is: 50%Si-12%Al 2O 3-18%C-20%SiC.Take by weighing Si powder (crossing 325 orders), the Al of aforementioned proportion 2O 3Powder (cross 325 orders), C powder (crossing 325 orders), SiC powder (crossing 325 orders) be take ethanol as dispersion agent, be placed in the planetary ball mill fully take out behind the mixing after dry stand-by.At last, the C/C matrix material is placed plumbago crucible, and with the powder of mixing it is buried fully, after crucible is put into High Temperature Furnaces Heating Apparatus, from room temperature to 1100 ℃, need 50min; Need 1.5h from 1100 ℃-1800 ℃; 1800 ℃ of insulation 1.5h, argon shield.Be cooling subsequently, need 1h from 1800 ℃ to 1200 ℃.Last furnace cooling.
After the SiC articulamentum prepares, in ultrasonic washing instrument, wash the powder that sticks on the sample with alcohol, and sample as in the baking oven 100 ℃ fully dry.To utilize chemical Vapor deposition process (CVD) preparation SiC middle layer subsequently.
Take MTS (trichloromethyl silane) as SiC source, H 2Be carrier gas, Ar is diluent gas, trichloromethyl silane is taken out of H from head tank with Bubbling method 2Regulate H as diluent gas simultaneously 2/ MTS ratio, various gases mix in mixed gas tank, are passed into the reaction zone of body of heater by bottom of furnace body again, after thermal degradation, after the residual gas filtration, are taken away by vacuum pump.Parameter is: H 2/ MTS=8 (mol ratio), Ar flow are 250mlmin -1, deposition pressure<1kPa.Heating is from room temperature to 300 ℃ in the reaction process, the 30min that takes time, 300 ℃ of insulation 1h; From 300 ℃-1200 ℃, need 1.5h; 1200 ℃ of insulation 6h pass into reactant gases therebetween; Be cooled to 400 ℃, need 1.2h from 1200 ℃.Last furnace cooling.
Be exactly to utilize spread coating and in-situ oxidation reaction method to prepare the ceramic systems external coating (EC) after the SiC middle layer prepares.
With high-purity α-Al 2O 3Powder and Y 2O 3Powder take mol ratio as preparation in 5: 3, adopts planetary high-energy ball mill, as medium mixed powder is carried out wet-milling with dehydrated alcohol, and ratio of grinding media to material is 4: 1, Ball-milling Time 32h.Ball milling is by calcining, from room temperature to 300 ℃, and the 30min that takes time, 300 ℃ of insulation 2h; From 300-1450 ℃, need 110min, 1450 ℃ of insulation 2h, furnace cooling makes yttrium aluminum garnet (YAG) powder.With SiC powder, YAG powder and the partially stabilized ZrO of yttrium oxide 2Powder (YSZ) was according to proportioning weighing in 75: 25: 5.Add (3wt%) solution preparation one-tenth brushing slurry of polyvinyl alcohol (PVA), powder and PVA volume ratio are 1: 2.Then slurry is brushed equably and had the SiC sample surfaces in internal layer and middle layer.Sample after the brushing is dried 4h in 100 ℃ of constant temperature ovens.Dried sample is positioned in the vacuum carbon tube furnace, uses argon shield, from room temperature to 300 ℃, and the 60min that takes time, 300 ℃ of insulation 1h; From 300-1450 ℃, need 110min, 1450 ℃ of insulation 1h; From 1450 ℃ to 600 ℃, need 80min.Then furnace cooling.At last, with above coating sample preoxidation 1-2h in 1500 ℃ of air, make ceramic coating very fine and close and that have good chemical and physical compatibility by the in-situ oxidation reaction.
Through the compound coating sample after 1500 ℃ of preoxidation through 150h, anti-oxidant test and 10 anti-thermal shock tests in 1500 ℃ of air, it is complete that coating keeps, do not occur coming off, fall the piece phenomenon, its quality change still is in the weightening finish state, and rate of body weight gain is 1.77%, and coating sample strength retention is 98.7%.
Embodiment 2
Adopt 70%Si-4%Al 2O 3-12%C-14%SiC investment prepares the SiC articulamentum, adopts parameter to be: H 2/ MTS=10 (mol ratio), Ar flow are 200mlmin -1, deposition pressure<1kPa, 1100 ℃ of insulation 8h prepare the SiC sealing ply.Adopt SiC powder, YAG powder and the partially stabilized ZrO of yttrium oxide 2Powder (YSZ) is according to the preparation ceramic outer coating of 60: 30: 10 proportionings, and all the other steps are the same.The coating sample that makes is through 150h, anti-oxidant test in 1500 ℃ of air, and it is complete that coating keeps, and do not occur coming off, and its oxidation weight gain rate is 0.35%, and coating sample strength retention is 96.8%.
Embodiment 3
Adopt 45%Si-10%Al 2O 3-10%C-35%SiC investment prepares the SiC articulamentum, adopts parameter to be: H 2/ MTS=12 (mol ratio), Ar flow are 180mlmin -1, deposition pressure<1kPa, 1000 ℃ of insulation 8h prepare the SiC sealing ply.Adopt SiC powder, YAG powder and the partially stabilized ZrO of yttrium oxide 2Powder (YSZ) is according to the preparation ceramic outer coating of 75: 25: 5 proportionings, and all the other steps are the same.The coating sample that makes is through 150h, anti-oxidant test in 1500 ℃ of air, and it is complete that coating keeps, and do not occur coming off, and its oxidation weight gain rate is 0.11%, and coating sample strength retention is 95.7%.

Claims (4)

1. the preparation method of the polynary composite ceramic coat of the long-time high-temperature oxidation resistant of carbon/carbon composite is characterized in that,
From inside to outside successively preparation on the carbon/carbon composite surface: articulamentum, sealing ply and ceramic coating, described articulamentum is the SiC layer of entrapping method preparation, described sealing ply is the SiC layer of chemical Vapor deposition process preparation, and described ceramic coating is the SiO of spread coating and the preparation of in-situ oxidation reaction method 2-Y 2Si 2O 7-ZrSiO 4-Al 2SiO 5Ceramic layer;
The concrete steps that described entrapping method prepares articulamentum are as follows:
According to the quality proportioning be: Si 40-75%, Al 2O 32-13%, C 8-20%, SiC10-38% take by weighing Si powder, Al 2O 3Powder, C powder, the SiC powder adds dispersion agent, takes out dry rear stand-by behind the abundant mixing of ball milling; At last, carbon/carbon composite is placed plumbago crucible, and with the powder of mixing it is buried fully, after crucible is put into High Temperature Furnaces Heating Apparatus, at 1700 ℃-2000 ℃ lower insulation 1.5-3h;
The concrete steps that described chemical Vapor deposition process prepares sealing ply are as follows:
Trichloromethyl silane is taken out of H from head tank with Bubbling method 2Mix in mixed gas tank with Ar, pass into again the chemical vapor deposition stove precursor reactant, H 2/ trichloromethyl silane mol ratio=6-12, Ar flow are 150-280mLmin -1, deposition pressure<1kPa; Temperature is 800 ℃-1280 ℃, soaking time 3-12h;
Described spread coating and in-situ oxidation reaction method prepare SiO 2-Y 2Si 2O 7-ZrSiO 4-Al 2SiO 5The concrete steps of ceramic layer are as follows:
SiC powder, YAG powder and YSZ powder are mixed according to quality 50-82:15-30:3-20 proportioning, add the PVA solution preparation and become to brush slurry, powder and PVA liquor capacity are than being 0.5-0.8; The PVA strength of solution is 2wt%-8wt%; Then slurry is brushed equably on the carbon/carbon composite surface with articulamentum and sealing ply; Sample oven dry after the brushing, high temperature sintering makes coating; At last, with its preoxidation 0.5-4h in 1300 ℃ of-1500 ℃ of air, make ceramic coating by the in-situ oxidation reaction.
2. the preparation method of polynary composite ceramic coat according to claim 1 is characterized in that, described Si powder, SiC powder, C powder, Al 2O 3Powder is all crossed 325 orders.
3. the polynary composite ceramic coat of the long-time high-temperature oxidation resistant of carbon/carbon composite is characterized in that, is the polynary composite ceramic coat that is prepared from by claim 1 or 2 described methods.
4. the application method of polynary composite ceramic coat claimed in claim 3 is characterized in that, is applied to prepare around the head of hypersonic vehicle and the non-direct ablation heat resistant structure spare of wing, and prepares the aeroengine thrust augmentation combustor material.
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