CN101135034B - Method for preparing oxidation resistant Ti-Al-Ag ternary coating - Google Patents
Method for preparing oxidation resistant Ti-Al-Ag ternary coating Download PDFInfo
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- CN101135034B CN101135034B CN200710046911A CN200710046911A CN101135034B CN 101135034 B CN101135034 B CN 101135034B CN 200710046911 A CN200710046911 A CN 200710046911A CN 200710046911 A CN200710046911 A CN 200710046911A CN 101135034 B CN101135034 B CN 101135034B
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Abstract
The process of preparing antioxidant ternary Ti-Al-Ag coating includes the following steps: 1. spray pelletizing to form spherical particle suitable for hot spraying with the material composite gamma-TiAl/Ag powder; 2. low pressure plasma spraying the powder to the surface of substrate to form gamma-TiAl/Ag coating; and 3. polishing the coating with waterproof abrasive paper and heat treatment inside a furnace first in vacuum and then under protection of filled Ar to obtain ternary Ti-Al-Ag coating. The present invention converts the composite powder into ternary alloy through vacuum heat treatment causing high temperature diffusion, and has simple technological process, low investment for apparatus and high coating preparing efficiency.
Description
Technical field
The present invention is a kind of preparation method of oxidation-resistant material technical field, specifically is a kind of preparation method of oxidation resistant Ti-Al-Ag ternary coating.
Background technology
Intermetallic compound γ-TiAl has the excellent high-temperature over-all properties, comprises that in certain temperature range the mechanical property of yield strength and Young's modulus is all comparatively outstanding.Its density is lower, specific tenacity is higher, is the alloy in lightweight of a kind of resistance toheat near superalloy, is considered to a kind of quality matetrial that is suitable for automobile, aerospace field.Yet γ-TiAl is at the medium-term and long-term mixed oxidization skin that can generate Al/Ti on the surface that exposes of the air more than 700 ℃, and this oxide skin is loosened, easily peeled off, and is helpless to promote the antioxidant property of matrix.But Shemet etc. discover, when the atomic percent about 50% of Al and content greater than Ti, and the γ-TiAl base alloy that contains Ag 2-5at.% has excellent antioxidant property.Be deposited on matrix if will contain γ-TiAl of a certain amount of Ag as coated material, can promote the antioxidant property of matrix undoubtedly.
Find through literature search prior art, Niewolak etc. are at ADVANCED ENGINEERINGMATERIALS (advanced engineering materials, " Alumina-formingcoatings for titanium and titanium aluminides (aluminum oxide that is fit to titanium alloy and titanium aluminum alloy forms coating) " of 3 the 7th phases of volume of calendar year 2001) delivering in matrix surface deposition one deck Ti-Al-Ag ternary alloy coating, will generate the fine and close α-Al of one deck with magnetically controlled sputter method on the surface soon after this ternary alloy exposes in 800 ℃ of air
2O
3Film effectively stops the further oxidation of matrix, has significantly improved the oxidation-resistance of matrix.Its weak point is: magnetron sputtering deposition efficient is very low, obtain the coating of adequate thickness under the actual condition, and production cost is high, so this method comparatively is suitable for laboratory applications, and is difficult to obtain industrialized popularization and use.
Summary of the invention
The present invention is directed to sputtering technology inefficiency cost problem of higher, proposed a kind of preparation method of oxidation resistant Ti-Al-Ag ternary coating.The present invention prepares carefully to 10 by ball grinding technique earlier
2Nm-10
1The uniform γ of μ m and particle distribution-TiAl/Ag composite granule, after the spray-drying process granulation, this composite granule can be by low-voltage plasma spraying deposition techniques efficiently to matrix surface, make the diffusion of Ag particle be dissolved in γ-TiAl matrix by thermal treatment then, form ternary Ti-Al-Ag alloy coat.Efficient height of the present invention, equipment and technology are simple, low production cost, 750-800 ℃ of atmospheric oxidn can form α-Al on the surface
2O
3The oxide film of base, thus significantly improve the antioxidant property of matrix in high temperature air.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
A) raw material adopts γ-TiAl and Ag composite granule, adopts atomizing granulating technology to obtain to be suitable for the spheroidal particle of thermospray;
Described γ-TiAl and Ag composite granule, be at first commercially available γ-TiAl powder (wherein the atomic percent of Al is 51-55%) and two kinds of raw materials of commercially available Ag powder to be mixed, make the mole number of Ag account for the 2-5% of Ti, Al, Ag element total mole number, mixed powder is carried out the wet method mechanical ball milling, dry, the fine powder that the acquisition of sieving mixes, i.e. γ-TiAl and Ag composite granule.
Described wet method mechanical ball milling is meant: with chemical pure ethanol or acetone is medium, and mixed powder is full of ball grinder with chemical pure ethanol or acetone diluted to pasty state, does not have the space to hold air in the feasible jar, perhaps remaining space is charged into the Ar gas shiled.Insert abrading-ball according to large, medium and small three kinds of specifications and carry out wet ball grinding, whole ball material mass ratio is 3-5: 1-2.
In the described wet method mechanical ball milling, abrading-ball divides large, medium and small three kinds, and mass ratio is respectively 3-5: 2-3: 5-2.
In the described wet method mechanical ball milling, three kinds of ball radius are respectively 8-15mm, 5-8mm and 2-5mm.
In the described wet method mechanical ball milling, the ball milling time is 12 hours-24 hours.
In the described wet method mechanical ball milling, ball milling frequency 〉=35HZ.
Described drying, its temperature are≤200 ℃.
Described sieving was meant 〉=300 mesh sieves.
Described commercially available γ-TiAl powder, its purity is greater than 2N5, particle diameter≤100 μ m.
Described commercially available Ag powder, its purity be greater than 2N5, particle diameter≤75 μ m.
Mixed powder is the thinnest behind ball milling to reach hundreds of nanometers, and mean particle size is about micron order.The spray-dried method of this composite granule is obtained to be suitable for the spheroidal particle of thermospray, and its granularity is 150 order to 300 orders.
B) adopt low-voltage plasma spraying that the gained composite granule is sprayed at matrix surface, obtain γ-TiAl/Ag coating;
Described low-voltage plasma hot-spraying techniques parameter is: the main air stream amount is 60 liters/minute, inferior airshed be the 25-30 liter/minute, arc current is the 550-600 ampere, arc voltage is a 50-60 volt, powder sending quantity is the 15-30 Grams Per Minute.
C) will spray good sample surfaces polishing and be placed in the stove, and fill Ar gas shiled thermal treatment after the first vacuum and obtain the Ti-Al-Ag ternary coating.
Fill Ar gas shiled thermal treatment after the described first vacuum, be specially: keep vacuum tightness＜10
-3Pa and temperature 500-600 ℃, charge into Ar to 1-3 normal atmosphere subsequently, meanwhile promote temperature to 700-750 ℃, insulation, the pressurize stove is cold.
Described keeping, its time is 10-30 minute.
Described insulation, its time is 3-5 hour.
When being exposed in the air, ternary Ti-Al-Ag alloy can the absorption owing to O generate Z phase (Al in nearly surface
3Ti
5O
2), cause the rich Al of the poor Ti of upper layer, thereby form rich Al during oxidation
2O
3Surface film oxide.Exist as long as Z is steady in a long-term mutually, the oxide film on surface is just with Al
2O
3Be main, thereby promote the antioxidant property of matrix.And Ag has played the effect of stable Z phase in the dissolving of Z in mutually, the simultaneously also indirect rich Al characteristic of having stablized surface film oxide, indirect lifting the antioxidant property of matrix.
Existing technology obtains the Ti-Al-Ag ternary alloy by vacuum melting earlier usually, further realizes follow-up preparation purpose then on this basis.By comparison, the present invention just simply carries out physical mixed with commercially available γ-TiAl and Ag, generates the Ti-Al-Ag ternary alloy by the heat treating method diffusion then.Because raw-material initial configuration is a powder, is particularly useful for preparing coating by hot-spraying techniques.By this invention, the coating of 200 μ m only needed just can obtain in 5 minutes, and coating and matrix especially with titanium alloy substrate bonding strength height, rapid shrend is cooled in the thermal shock test of room temperature after 750 ℃ are incubated 30 minutes, the life-span of coating reaches 10
2The order of magnitude.In the oxidation-resistance test, the oxidation weight gain of coating coating after exposing 100 hours under 750 ℃ of air only is 2mg/cm
2About, compare than the antioxidant property of titanium alloy substrate and to improve a lot.So preparation technology of the present invention is simple, equipment drops into less and suitable large-scale industrial production.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
γ-TiAl powder purity 99.95%, 30-50 μ m, wherein the Al element accounts for TiAl alloy atom per-cent 55%.Ag purity 99.95%, the 30-50 micron.Two kinds of powders being mixed 5% of the total mole number that makes the mole number of Ag account for Al, Ti, three kinds of elements of Ag, is the medium wet ball grinding with chemical pure ethanol, and frequency is 35HZ, ratio of grinding media to material 3: 2, and mechanical ball milling 12 hours, 100 ℃ of dryings, vibration sub-sieve 300 orders sieve.The technical indicator of resulting γ-TiAl and Ag composite granule is: γ-TiAl particle diameter is the 0.1-5 micron, and the Ag particle diameter is the 0.5-5 micron, and the Ag uniform particles is distributed in γ-TiAl particle, perhaps becomes larger particles with γ-TiAl is chimeric.Above-mentioned composite granule is prepared the powder that is suitable for spraying usefulness by the atomization drying method, by the vacuum plasma spray coating deposition techniques in titanium alloy substrate, the vacuum plasma spray coating parameter is: the main air stream amount is 60 liters/minute, inferior airshed is 25 liters/minute, arc current is 560 amperes, arc voltage is 50 volts, and powder sending quantity is 15 Grams Per Minutes, obtains γ-TiAl and Ag composite granule coating at matrix surface.After the cooling sand paper of coatingsurface with 800# is polished, place vacuum tightness 10
-3In the stove of Pa, temperature is set at 550 ℃ and kept 10 minutes, charges into Ar to 3 normal atmosphere subsequently, meanwhile promotes temperature to 700 ℃, is incubated 4 hours, obtains ternary Ti-Al-Ag coating.
This coating 750 ℃ of oxidation 10-16 hour rear surfaces in air generate rich alumite, coating weightening finish 2.1mg/cm after 100 hours
2
Embodiment 2:
γ-TiAl powder purity 99.9%, 50-70 μ m, wherein the Al element accounts for TiAl alloy atom per-cent 53%.Ag purity 99.9%, the 50-70 micron.Two kinds of powders being mixed 3% of the total mole number that makes the mole number of Ag account for Al, Ti, three kinds of elements of Ag, is the medium wet ball grinding with chemical pure ethanol, and frequency is 40HZ, ratio of grinding media to material 3: 2, and mechanical ball milling 16 hours, 200 ℃ of dryings, vibration sub-sieve 300 orders sieve.The technical indicator of resulting γ-TiAl and Ag composite granule is: γ-TiAl particle diameter is the 1-5 micron, and the Ag particle diameter is the 1-5 micron, and the Ag uniform particles is distributed in γ-TiAl particle, perhaps becomes larger particles with γ-TiAl is chimeric.Above-mentioned composite granule is prepared the powder that is suitable for spraying usefulness by the atomization drying method, by the vacuum plasma spray coating deposition techniques in titanium alloy substrate, the vacuum plasma spray coating parameter is: the main air stream amount is 60 liters/minute, inferior airshed is 25 liters/minute, arc current is 560 amperes, arc voltage is 50 volts, and powder sending quantity is 15 Grams Per Minutes, obtains γ-TiAl and Ag composite granule coating at matrix surface.After the cooling sand paper of coatingsurface with 800# is polished, place vacuum tightness＜10
- 3In the Pa stove, temperature is set at 550 ℃ and kept 30 minutes, charges into Ar to 2 normal atmosphere subsequently, meanwhile promotes temperature to 700 ℃, is incubated 4 hours, obtains ternary Ti-Al-Ag coating.
This coating 750 ℃ of oxidation 10-16 hour rear surfaces in air generate rich alumite, coating weightening finish 3.5mg/cm after 100 hours
2
Embodiment 3:
γ-TiAl powder purity 99.5%, 70-100 μ m, wherein the Al element accounts for TiAl alloy atom per-cent 51%.Ag purity 99.5%, the 70-100 micron.Two kinds of powders being mixed 2% of the total mole number that makes the mole number of Ag account for Al, Ti, three kinds of elements of Ag, is the medium wet ball grinding with chemical pure ethanol, and frequency is 45HZ, ratio of grinding media to material 3: 1, and mechanical ball milling 24 hours, 100 ℃ of dryings, vibration sub-sieve 300 orders sieve.The technical indicator of resulting γ-TiAl and Ag composite granule is: γ-TiAl particle diameter is the 1-20 micron, and the Ag particle diameter is the 1-20 micron, and the Ag uniform particles is distributed in γ-TiAl particle, perhaps becomes larger particles with γ-TiAl is chimeric.Above-mentioned composite granule is prepared the powder that is suitable for spraying usefulness by the atomization drying method, by the vacuum plasma spray coating deposition techniques in titanium alloy substrate, the vacuum plasma spray coating parameter is: the main air stream amount is 60 liters/minute, inferior airshed is 25 liters/minute, arc current is 560 amperes, arc voltage is 50 volts, and powder sending quantity is 15 Grams Per Minutes, obtains γ-TiAl and Ag composite granule coating at matrix surface.After the cooling sand paper of coatingsurface with 800# is polished, place vacuum tightness＜10
-3In the Pa stove, temperature is set at 550 ℃ and kept 15 minutes, charges into Ar to 1.2 normal atmosphere subsequently, meanwhile promotes temperature to 700 ℃, is incubated 4 hours, obtains ternary Ti-Al-Ag coating.
This coating 750 ℃ of oxidation 10-16 hour rear surfaces in air generate rich alumite, coating weightening finish 2.9mg/cm after 100 hours
2
Claims (8)
1. the preparation method of an oxidation resistant Ti-Al-Ag ternary coating is characterized in that, may further comprise the steps:
A) raw material adopts the used for hot spraying spheroidal particle powder that γ-TiAl and Ag are composited, its preparation technology is: at first γ-TiAl powder and two kinds of raw materials of Ag powder are mixed, the atomic percent of Al is 51-55% in the γ that is adopted-TiAl powder, the mole number of Ag accounts for the 2-5% of Ti, Al, Ag element total mole number in the mixed powder, mixed powder is carried out the wet method mechanical ball milling, dry, sieving, acquisition mixes, mean particle size is micron-sized γ-TiAl and the Ag composite granule, adopts atomizing granulating technology that composite granule is processed into used for hot spraying spheroidal particle powder then;
B) adopt low-voltage plasma spraying that gained spheroidal particle powder is sprayed at matrix surface, obtain γ-TiAl/Ag coating;
C) will spray good sample surfaces polishing and be placed in the stove, and fill Ar gas shiled thermal treatment after the first vacuum and obtain the Ti-Al-Ag ternary coating;
Described low-voltage plasma spraying processing parameter is: the main air stream amount is 60 liters/minute, inferior airshed be the 25-30 liter/minute, arc current is the 550-600 ampere, arc voltage is a 50-60 volt, powder sending quantity is the 15-30 Grams Per Minute;
Fill Ar gas shiled thermal treatment after the described first vacuum, be specially: keep vacuum tightness＜10
-3Pa and temperature 500-600 ℃, charge into Ar to 1-3 normal atmosphere subsequently, meanwhile promote temperature to 700-750 ℃, insulation, the pressurize stove is cold.
2. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1; it is characterized in that; described wet method mechanical ball milling; be meant: with chemical pure ethanol or acetone is medium; mixed powder is full of ball grinder with chemical pure ethanol or acetone diluted to pasty state, does not have the space to hold air in the feasible jar, perhaps remaining space is charged into the Ar gas shiled; insert abrading-ball according to large, medium and small three kinds of specifications and carry out wet ball grinding, whole ball material mass ratio is 3-5: 1-2.
3. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1 and 2, it is characterized in that in the described wet method mechanical ball milling, abrading-ball divides large, medium and small three kinds, mass ratio is 3-5: 2-3: 5-2, and three kinds of ball radius are respectively 8-15mm, 5-8mm and 2-5mm.
4. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1 and 2 is characterized in that, in the described wet method mechanical ball milling, the ball milling time is 12 hours-24 hours, ball milling frequency 〉=35Hz.
5. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1 is characterized in that, described drying, its temperature are≤200 ℃; Described sieving was meant 〉=300 mesh sieves.
6. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1 is characterized in that, described used for hot spraying spheroidal particle powder, and its granularity is 150 order to 300 orders.
7. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1 is characterized in that, described keeping, and its time is 10-30 minute.
8. the preparation method of oxidation resistant Ti-Al-Ag ternary coating according to claim 1 is characterized in that, described insulation, and its time is 3-5 hour.
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