CN1422974A - Coating formula for preventing surface corrosion of gas turbine blade and process therefor - Google Patents
Coating formula for preventing surface corrosion of gas turbine blade and process therefor Download PDFInfo
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- CN1422974A CN1422974A CN01139075A CN01139075A CN1422974A CN 1422974 A CN1422974 A CN 1422974A CN 01139075 A CN01139075 A CN 01139075A CN 01139075 A CN01139075 A CN 01139075A CN 1422974 A CN1422974 A CN 1422974A
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Abstract
There is a coat prescription which can resist the corrosion of gas turbine vane surface and the craft; it applies to gas turbine vane which uses cheap fuel. The steps are: the MCrAlY is painted on the surface of vane to enhance the adhesion, then the vane is heated to 1200 C degree, it is painted with 1-4 micron multiaperture ceramics by plasma plating method, then it is plated with thick ceramics. The multiaperture ceramics and thick ceramics are all zirconia which is stabilized by yttria. The temperature of vane is controlled about 500 C degree. The material of vane can use nickek base super heat-resisting alloy.
Description
Technical field:
The present invention relates to a kind of protection gas turbine blades, coating formula that prolongs its work-ing life and technology, especially a kind of anti-surperficial sprayed-out recipe and technology of peeling off ceramic coating.
Background technology:
In the internal combustion turbine that uses cheap fuel,, can on blade, form the very strong melting salt settling of corrodibility because partial blade is operated in different temperature ranges, and contains the vanadate objectionable impurities in the fuel.Prior art adopts diffusion coating (calorize platinum) to make top coat in order to reduce the corrodibility to blade.Utilize sealing diffusion, plasma spray coating, the spraying plating of electron beam direct steam, perhaps use high chromium or contain the coating of precious metal, apply whole aerofoil and reach corrosion-resistant.But on the surface of these metallic coatings, rose vitriol-nickel and sodium sulfate form liquid film, the base alloy of meeting heavy corrosion coating final etching blade.In addition, some coating is Co, Cr, AI and platinum oxide for example, poor ductility under the temperature about 1300 ℃, and can break makes molten sulfate contact with base alloy under the high stress.Because this scope is consistent with high stress areas, the additive effect of corrosion and stress can cause the reduction of surperficial mechanical property, just is commonly referred to II-type low temperature thermal etching process.
In addition, also have a kind ofly in gas turbine blades surface-coated thermal barrier technology, though that this coating has is corrosion-resistant, coating is quite thick, and purpose is to form temperature drop between air-flow and metal blade.Generally by the top ceramic layer of densification, porous ceramics middle layer and MCrAIY (M herein is cobalt and nickel) key coat constitutes this thermal barrier, and its typical thickness is the 20-30 micron.But the defective of this coating is; Be easy to generate the crack in the coating and cause peeling off, adsorbed corrosive compound on the contrary deleterious melting salt one class in blade metallic surface.
Summary of the invention:
The objective of the invention is, improve the top coat of existing gas turbine blades, it is good to make it under 1300 ℃ of temperature ductility, leakless, and the melting salt settling is had very strong antistripping and solidity to corrosion, do not produce the thermal etching of II-type low temperature, prolong blade work-ing life.
The technical scheme that the present invention solves the problems of the technologies described above employing is;
Reach in the gas turbine blades temperature and can have low-melting vitriol, when vanadate and muriate, unexpected is to break not too easily in the ceramic blocking layer of 1-4 micron thickness.Its concrete coating processes is, at first on blade airfoil, apply the undercoat that strengthens sticking power and make key coat, the material of this key coat is that any aluminum oxide when being higher than 1100 ℃ of temperature forms thing. according to the experiment comparing result, this key coat material is MCrAIY preferably.Find that according to a large amount of experiment contrast make coating keep very thin and ceramic coating is coated in the coating procedure of blade, the temperature of blade is controlled at least 1200 ℃, this life-span for coating is most important.Its concrete coating processes is should pass through the key coat of a low pressure or a class technology applying coating such as argon shield and plasma spraying, so that metal bonding layer inside has minimum microstructure in conjunction with the space.This key coat should be about 5 micron thickness, by modes such as sputter or ion plating and the spraying platings of electron beam direct steam, forms above-mentioned key coat.This key coat has certain ductility at 1100 ℃ of suitable cold zones, should melt the sedimental chemical etching of vitriol by refractory.Apply porous ceramics again in the key coat outside then, at last at the outer ceramic of compact that applies of porous ceramics.Porous ceramics and ceramic of compact all pass through the zirconium white that yttria-stabilized is handled.Porous part is a zone of transition, and what thermal expansivity it does not almost have, because it is very thin, does not also have heat insulating ability.
The ceramic coating of 1-4 micron thickness as thin as a wafer is a suitable antistripping and corrosion resistant, and this coating is not as thermal barrier, because its thickness low LCL can not cause suitable temperature drop.
Porous ceramics plays the effect of a so-called thermal expansion transition, and its thickness also is quite thin.In addition, this ceramic coating must impermeabilisation, should enough alkali-alkaline-earth oxide-vanadate settling be kept apart with the cobalt oxide and the nickel oxide that can form at coated substrate contact surface place, thereby prevent to form rose vitriol and single nickel salt.In addition, if because the existence of lead, zinc, cadmium, manganese and vanadium (also possibility copper and phosphorus), and form more low-melting vitriol base fluid body.The pottery blocking layer must be with the same substrate isolation of aforesaid liquid, and ceramic blocking layer self also is the chemically-resistant etch to this corrosive liquid.
The material of blade is designed to be able to work in-1500 ℃ of degree of 1100 ℃ of degree temperature range at least, and be designed to be able to use impure fuel, its main points are, blade reaches at least about 1200 ℃ in temperature, the ceramic coating of coating 1-4 micron thickness in the working order, makes the stress of ceramic coating inside remain in the compressed state in 1250 ℃-1500 ℃ degree temperature ranges.
Beneficial effect of the present invention is made strong explanation by following routine contrast experiment.Hollow superalloy Cylinder is applied the nickelalloy key coat of 5 micron thickness, and above-mentioned nickel alloy layer calculates according to weight, contains 20% chromium, 10% aluminium and about 0.5% yttrium.Apply the zirconium white of one deck 8%, the ceramic layer of yttrium oxide plasma spraying then.A cylindrical coat-thickness is 4 microns, and second cylindrical coat-thickness is 12 microns.
Above-mentioned sample is fixed with the air cooled anchor clamps, be positioned in the combustion unit, and, test the sample of coated ceramic with dashing with the products of combustion that sea salt and admixture sea salt and two kinds of plumbous No. 2 distillate fuels produce.Uncoated superalloy sample covers MCrAIY composition and various diffusion coating (calorize chromium, aluminium and calorize platinum) with the low pressure plasma spraying.Gas temperature is remained on 1900 ℃, and metal temperature is between 1100 ℃ to 1500 ℃.Feed the thermal cycling air-flow, air-flow is heated 55 minutes and forces cooling 5 minutes, and sample is tested 300 hours (being in all the time in the thermal cycling process) and tested.The time that the ceramic coating of 12 micron thickness begins to peel off is 100 hours, and the ceramic coating of 4 micron thickness finished up to test in 300 hours, had kept out all the time and had peeled off.The vitriol settling that peels off in the zone in 12 micron thickness coatings has demonstrated the visible marks of reacting with key coat, the coating of 4 micron thickness do not see fully peel off or with the sedimental reflection of sulfuric acid alkali.The superalloy of uncoated pottery and metal-superalloy demonstrate II-type corrosion in various degree.Best key coat metal composites is to contain (calculating by weight) 20% cobalt, 40% chromium, the nickel of 5.5% aluminium and 0.5% yttrium through plasma spraying.In addition, also can use the nickel that contains 30% cobalt, 23% chromium, 8.5% aluminium and 0.5% yttrium, and other key coat that contains iron one class of chromium, aluminium and yttrium.
Description of drawings:
The invention will be further described below in conjunction with drawings and Examples.
Accompanying drawing is the cross section that blade has applied protective layer.
In the accompanying drawing, the 1st, gas turbine blades, the 2nd, key coat on the blade airfoil, the 3rd, the porous expanding layer, the 4th, fine and close outer.
Embodiment:
On blade shown in the drawings, at first apply the MCrAIY key coat, heat blade then to about 1200 ℃, apply porous ceramics then, and then apply ceramic of compact, porous ceramics and ceramic of compact all are the zirconium whites of handling through stabilized with yttrium oxide.In the process that applies porous ceramics and ceramic of compact, the temperature of blade is controlled at 1200 ℃ all the time.
With reference to accompanying drawing, 1 expression gas turbine blades has key coat 2 in the cross section on the airfoil portion of blade, porous expanding layer 3 and fine and close skin 4, and the root of blade is applying coating not.Because the aerofoil Lower Half is a critical area, the most of operating temperature range in this zone requires a Lower Half at the most close airfoil portion root to apply coating of the present invention at 1250 ℃-1500 ℃.Blade mean no matter be motion or immobilized, being sometimes referred to as the slurry wing is stationary part, often adopt cobalt-based super heat-resistant alloy, and motion parts is a nickel-base heat resisting superalloy.
1100 ℃ of-1500 ℃ of temperature ranges, II-type low temperature thermal etching process has taken place to be commonly referred in blade airfoil, because this scope is consistent with high stress areas, the additive effect of corrosion and stress causes the reduction of the mechanical property of the responsive part of blade surface.The key coat of blade should have suitable low temperature (being lower than 1100 ℃) ductility, should melt the sedimental chemical erosion of vitriol by refractory, and should be the aluminum oxide formation thing when being higher than 1100 ℃ of temperature.These compositions comprise: the Ni-based NiCrAlY key coat of (calculating according to weight) 20% cobalt, 40% inscription, 5.5% aluminium, 0.5% yttrium (under the condition that does not have the silicon additive), also can use the FeCrAlY key coat.
The ceramic segment that applies also can be the zirconium white of handling through yttria-stabilized.Preferably the pottery of the plasma spray coating of quite anti-cyclic thermal stres contains the 20% porosity hot coating of (referring to volume), has best thermal-shock resistance.Show the phase in use longevity under the lower porosity meeting shortening heat stress.When taking all factors into consideration the blocking layer effect, if the void distribution of ceramic coating with the junction, metallic surface, and coating inside has the hole of thermal stress resistance, then ceramic segment need have the porous tight zone simultaneously.Can pass through the plasma spraying of control fine particle pottery, or by applying individual layer overbrushing layer, laser dissolves the surface then provides fine and close skin, thereby realizes above-mentioned requirements.
Ceramic composition is not limited to the zirconium white that stabilized with yttrium oxide is handled, also can be aluminum oxide, calcium oxide-zirconium dioxide, magnesium oxide-zirconium dioxide or other complexing ceramic oxide, this complexing ceramic oxide has quite stable in temperature during up to 1450 ℃, and also demonstrates chemical stability in sodium sulfate-plumbous oxide-sodium oxide melting salt.
Show that according to the experiment comparative analysis ceramic coating minimum thickness is necessary for 1 micron, maximum ga(u)ge is necessary for 4 microns.Porous part should be between 0.5 micron and 3.5 microns, and tight section should be between 0.5 micron.
The coated ceramic partial blade preheats more than 1100 ℃, is under the top temperature for use afterwards, because thermal expansion inequality between pottery and the base alloy makes blade lower section pottery be in the small compressed state earlier.The tendency of peeling off of ceramic coating reduces to minimum in thermal cycling and use like this.The antistripping that Here it is this thin layer shows than thick coating.During according to the methods described herein coated ceramic, the strain of ceramic coating during operation is the limit recoverable strain (nominally be 0.4% strain) less than porous ceramics.
Preferably only be lower than coated ceramic coating on about 1500 ℃ blade that part of in the working temperature of design.For reaching this purpose, can will not need the surf zone of coating to seal.The coating that applies according to the plasma spraying method has surperficial above slightly being pickled with grains or in wine of 100RMS.Be easy to contaminated surface during operation.If the foreign matter that exists fails to bring into play or burn, will increase the chance of ceramic blocking layer early failure under surface temperature.These materials are hydrocarbon polymer, lead, zinc, copper and halogen salt.Thick poor surface also can capture impingment particle, thereby increases settling accumulative speed.This can influence the gasdynamics of thermal conduction and air-flow.Because fine and close external coating (EC) might move.So should carefully carry out any precision work (not should gyro-finishing coating) of ceramic coating.If need really to carry out bigger last precision work, just must refill external coating (EC), to prevent hole.
Although thin ceramic coating and thick coating relatively are difficult for breaking, if exist adaptability to changes to surpass the effective elasticity limit of coating in blade metal composites inside, coating still may be broken.In fact.It is higher coating should not to be coated to working temperature, makes coating produce than hightension and strain and surpasses effective elasticity ultimate zone.Coating can be in a kind of compressed state a little less than service temperature the time.Underlayer temperature can be greater than 1200 ℃, and only are subjected to the restriction of temperature to the effect of base alloy.Above-mentioned thin ceramic coating is applied to coating and will still remains in compression or the zone during small tension state temperature, so that adapt to subsequently because the different heat expansion when heating, the strain that coated ceramic heating substrate produces.When applying coating, usually coating only should be coated in working temperature than underlayer temperature height less than 200 ℃-300 ℃ the zone in (thereby, if coated ceramic under 1600 ℃ underlayer temperature condition, coating only should be coated in working temperature and be lower than in 1900 ℃ the zone, preferably be lower than in 1850 ℃ the zone).If when very approaching top temperature, apply, then can apply whole aerofoil.
Coating processes of the present invention is to aim at rotating part and design, because these part time jobs are in the additional stress of high-speed rotation, but also can be used for the anticorrosion of stationary components.
Claims (7)
1. the coating formula and the technology that stop the gas turbine blades surface corrosion, the common working temperature of blade remain in 1100 ℃-1500 ℃ the scope.And suit to use the cheap fuel that contains corrosive impurity, it is characterized in that: the temperature that heats above-mentioned blade is controlled at least 1200 ℃ of scopes, has sprayed the ceramic coating of one deck 1-4 micron thickness on the surface of above-mentioned blade at least.
2. blade according to claim 1 is characterized in that, before the coated ceramic coating, at first will apply the key coat that strengthens sticking power on the blade metallic surface, and this key coat is that any aluminum oxide during greater than about 1100 ℃ of temperature forms thing.
3. according to the technology of claim 2, it is characterized in that key coat is MCrAlY.
4。Technology according to claim 1 and 2 and 3 is characterized in that, the pottery of 1-4 micron thickness is the zirconium white of handling through yttria-stabilized.
5. according to the technology of claim 1 and 2 and 3, it is characterized in that, by plasma spraying method coated ceramic coating.
6. according to the technology of claim 1 or 2, it is characterized in that, make blade with nickel-base heat resisting superalloy.
7. according to the technology of claim 1 or 2, it is characterized in that above-mentioned ceramic coating is in up at least 1200 ℃ of temperature ranges, ceramic coating still remains in the compression shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01139075A CN1422974A (en) | 2001-12-06 | 2001-12-06 | Coating formula for preventing surface corrosion of gas turbine blade and process therefor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN01139075A CN1422974A (en) | 2001-12-06 | 2001-12-06 | Coating formula for preventing surface corrosion of gas turbine blade and process therefor |
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| CN1422974A true CN1422974A (en) | 2003-06-11 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419219C (en) * | 2006-12-22 | 2008-09-17 | 西安陕鼓动力股份有限公司 | Surface composite coating of turbomachine rotor blade and preparation method thereof |
| US7597934B2 (en) | 2006-02-21 | 2009-10-06 | General Electric Company | Corrosion coating for turbine blade environmental protection |
| CN101611171B (en) * | 2006-04-06 | 2012-11-28 | 西门子公司 | Layered thermal barrier coating with a high porosity, and a component |
| CN110158032A (en) * | 2019-05-09 | 2019-08-23 | 成都超纯应用材料有限责任公司 | A kind of corrosion-resistant finishes and preparation method thereof |
-
2001
- 2001-12-06 CN CN01139075A patent/CN1422974A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7597934B2 (en) | 2006-02-21 | 2009-10-06 | General Electric Company | Corrosion coating for turbine blade environmental protection |
| US7993759B2 (en) | 2006-02-21 | 2011-08-09 | General Electric Company | Corrosion coating for turbine blade environmental protection |
| CN101611171B (en) * | 2006-04-06 | 2012-11-28 | 西门子公司 | Layered thermal barrier coating with a high porosity, and a component |
| CN100419219C (en) * | 2006-12-22 | 2008-09-17 | 西安陕鼓动力股份有限公司 | Surface composite coating of turbomachine rotor blade and preparation method thereof |
| CN110158032A (en) * | 2019-05-09 | 2019-08-23 | 成都超纯应用材料有限责任公司 | A kind of corrosion-resistant finishes and preparation method thereof |
| CN110158032B (en) * | 2019-05-09 | 2021-09-28 | 成都超纯应用材料有限责任公司 | Corrosion-resistant coating and preparation method thereof |
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