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CN105239049B - Al Y-gradients protection alloy coat of γ TiAl alloys surface refractory oxidation and preparation method thereof - Google Patents

Al Y-gradients protection alloy coat of γ TiAl alloys surface refractory oxidation and preparation method thereof Download PDF

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CN105239049B
CN105239049B CN201510659228.6A CN201510659228A CN105239049B CN 105239049 B CN105239049 B CN 105239049B CN 201510659228 A CN201510659228 A CN 201510659228A CN 105239049 B CN105239049 B CN 105239049B
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alloy
tial
target
gradients
burner hearth
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CN105239049A (en
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梁文萍
夏金姣
缪强
任蓓蕾
徐一
胡荣耀
李柏强
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Nanjing University of Aeronautics and Astronautics
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Abstract

The present invention discloses Al Y-gradients protection alloy coat of a kind of γ TiAl alloys surface refractory oxidation and preparation method thereof, and uniformly sputtering Al and Y-ion, technical process on γ TiAl alloys surface using magnetically controlled sputter method includes:(1) preheating, purified treatment:Al y alloys target and γ TiAl alloys are placed in burner hearth, adjust distance 15mm between target and γ TiAl alloys.Vacuum in burner hearth is evacuated to 10 first‑4Pa, argon gas is passed through, pressure in burner hearth is maintained at 0.45Pa.Bias is imposed to Al y alloy targets, processing time ensures in 10min, carries out ion(ic) etching and cleaning to γ TiAl alloys, purifies surface;(2) by distance controlling between Al y alloys target and γ TiAl alloys, pressure control is in 0.3~0.5Pa in 15~25mm, burner hearth, and in 150~250W, preparation time is controlled in 3~5h for target power control, so as to obtain Al Y-gradients protection alloy coat.Al Y-gradients protection alloy coat produced by the present invention and γ TiAl alloy binding abilities are good, and surfacing is fine and close, and γ TiAl alloys can be effectively protected under the conditions of high-temperature service.

Description

Gamma-TiAl alloy surface refractory oxidation Al-Y gradients protection alloy coat and its Preparation method
Technical field:
The present invention relates to metal surface properties modification technology, more particularly to a kind of gamma-TiAl alloy surface refractory oxidation Al-Y gradients protection alloy coat and preparation method thereof.
Background technology:
The comprehensive mechanical property that gamma-TiAl alloy has had, such as ductility, intensity and creep-resistant property, density is Ni-based conjunction The half of gold, but there is similar mechanical behavior under high temperature, therefore be with a wide range of applications therewith.But gamma-TiAl alloy is 700 The oxide skin(coating) in hierarchy occurs in hot environment more than DEG C:Outer layer is TiO2Layer, the Ti oxides of internal layer with Al2O3Mixture layer form, and internal oxide skin(coating) fails to form effective obstruction to diffusion process than more loose, this It is considered as the main reason for antioxygenic property is poor under TiAl alloy high temperature.
Process for modifying surface can improve gamma-TiAl alloy high temperature oxidation resistance on the premise of not affecting the mechanical properties. Wherein aluminized coating is that a kind of Al content that substrate material surface is improved by Al atoms permeatings reaches to form facing for oxide Boundary's content, so as to form rich Al metallic compound in substrate material surface.It is placed under oxidation environment, Al atoms and O atom knot Conjunction forms Al2O3。Al2O3Dense structure, have self-repairability concurrently again, the inoxidizability of matrix can be effectively improved.But aluminized coating by Mismatch in thermal coefficient of expansion, easily cracked in coat inside, these crackles provide passage for O atom diffusion, finally lead Coating is caused to lose the protective effect to matrix.
The method for improving aluminized coating is to prepare modified aluminide coating, such as Al-Cr, Al-Si by multicomponent thermochemical treatment technology And Al-Ti etc., by improving the adhesion of coating and matrix, improve antioxygenic property.But these coatings all come with some shortcomings, Such as Al-Cr coatings occur in oxidizing process coating thicken, precipitated phase precipitation coarsening phenomenon;Between Al-Si coatings and matrix Larger thermal stress be present, produce transversal crack, the oxidation later stage can lose protective effect to matrix etc..Lacking one kind at present can Aluminized coating adhesion is effectively improved, promotes the Al of continuous protectiveness2O3Modified aluminide coating of generation and preparation method thereof.
The content of the invention:
It is contemplated that improving the high temperature oxidation resistance of gamma-TiAl alloy, aluminium can be effectively improved by providing one kind Coating binding force, the modified aluminide coating for promoting the Al2O3 of continuous protectiveness to generate are that is, first using rare earth is added in fine aluminium Plain yttrium, to improve the adhesion of aluminized coating and high temperature oxidation resistance, the final service temperature for improving gamma-TiAl alloy.
The present invention adopts the following technical scheme that:A kind of Al-Y gradients protection of gamma-TiAl alloy surface refractory oxidation is closed Gold plating, from outward appearance to inner essence successively include sedimentary, diffusion layer, base layer three parts, it is described deposition composition of layer be Al65~ 30~35wt% of 70wt%, Y is formed;It is described diffusion composition of layer be 38~60wt% of Al, 0.3~27wt% of Y, Ti13~ 61wt%.
Further, the Al-Y gradients protection alloy coat thickness is 40~60 μm.
The present invention also adopts the following technical scheme that:A kind of Al-Y gradients protection of gamma-TiAl alloy surface refractory oxidation The preparation method of alloy coat, it comprises the following steps:
(1) aluminum melting:Technical pure aluminium ingot is added in graphite crucible, is placed in 700~800 DEG C of heating environments, constant temperature insulation 30min, while remove the oxide on molten aluminum liquid surface;
(2) yttrium is melted:Yttrium block is added in feeder, then adds in graphite crucible, is placed in 700~800 DEG C of heating environments It is interior, constant temperature insulation 30min, while remove the oxide on melting yttrium liquid surface;
(3) mixed melting liquid:The aluminium liquid of molten state and yttrium liquid are poured into same graphite crucible, are stirred continuously mixed liquor, Al and Y is carried out alloying reaction, turn into alloying liquation
Alloying reaction:Al+Y→AlY;
(4) target is prepared:Mixing AlY alloy solutions are stood into 30min, will after being then gradually cooled to 680~700 DEG C Molten alloy liquid is poured into mould, pours into 100 × 3mm of Ф circular target;
(5) matrix material pre-processes:Prepare gamma-TiAl alloy, polishing, flannelette are polished to nothing and drawn step by step on abrasive paper for metallograph After the preferable burnishing surface of trace, it is placed in alcohol and is cleaned by ultrasonic;
(6) preheating, purified treatment:Al-Y alloy target materials and gamma-TiAl alloy are placed in burner hearth, regulation target and γ- Distance 15-20mm between TiAl alloy, vacuum in burner hearth is evacuated to 10 first-4Pa, argon gas is passed through, is maintained at pressure in burner hearth 0.3-0.5Pa, bias is imposed to Al-Y alloy target materials, processing time ensures in 10-20min, and ion is carried out to gamma-TiAl alloy Etching and cleaning, purify surface;
(7) magnetron sputtering Al-Y alloy coats:By distance controlling between Al-Y alloy target materials and gamma-TiAl alloy 15~ 25mm, in burner hearth pressure control in 0.3~0.5Pa, target power control in 150~300W, preparation time control in 3~5h, So as to obtain Al-Y alloy coats;
(8) diffusion in vacuum is annealed:Obtained Al-Y alloy coating materials are placed in vacuum atmosphere oven and carry out diffusion in vacuum Annealing, at 600~800 DEG C, soaking time is controlled in 2~3h, subsequent furnace cooling for treatment temperature control.
The present invention has the advantages that:Compared with other modified aluminide coatings described in background technology, the present invention Obtained Al-Y gradients protection alloy coat is due to addition rare earth element y and diffusion annealing processing, and acquisition particle is tiny, and distribution is equal It is even, and it is Al and Al to form extexine3Y, composition form continuous graded with gamma-TiAl alloy, and binding ability is good, Oxidation-resistance property strengthens at 650~850 DEG C.And the technique for preparing Al-Y alloy coats is simple, efficiency high and repeatability The features such as strong.
Brief description of the drawings:
Fig. 1 is the SEM figures that Al-Y gradients produced by the present invention protect that alloy coat surface amplifies 500 times.
Fig. 2 is the SEM figures that Al-Y gradients produced by the present invention protect that alloy coat surface amplifies 5000 times.
Fig. 3 is the SEM figures that Al-Y gradients produced by the present invention protect that alloy coat section amplifies 1000 times.
Fig. 4 is that Al-Y gradients produced by the present invention protect alloy coat cross sectional elements to be distributed EDS collection of illustrative plates.
Fig. 5 is that Al-Y gradients produced by the present invention protect alloy coat surface XRD spectrum.
Fig. 6 is that surface SEM schemes after Al-Y gradients produced by the present invention protect 650 DEG C of cyclic oxidation 100h of alloy coat.
Fig. 7 is that surface SEM schemes after Al-Y gradients produced by the present invention protect 750 DEG C of cyclic oxidation 100h of alloy coat.
Fig. 8 is that surface SEM schemes after Al-Y gradients produced by the present invention protect 850 DEG C of cyclic oxidation 100h of alloy coat.
Embodiment:
The Al-Y gradients protection alloy coat of gamma-TiAl alloy surface refractory oxidation of the present invention from outward appearance to inner essence includes successively Sedimentary, diffusion layer, base layer three parts, wherein deposition composition of layer forms for 65~70wt% of Al, 30~35wt% of Y;Expand It is 38~60wt% of Al, 0.3~27wt% of Y, 13~61wt% of Ti to dissipate composition of layer, and composition changes in gradient, Al and Y contents Slowly decline, Ti contents slowly rise, and jumping phenomenon is not present in elemental composition, illustrates Al-Y alloy coats and γ-TiAl (Ti-23.9Al-2.4Cr-0.9Nb) alloy realizes metallurgical binding, and binding ability is good;Al-Y gradients protect alloy coat thickness For 40~60 μm.
The preparation method of the Al-Y gradients protection alloy coat of gamma-TiAl alloy surface refractory oxidation of the present invention, it is adopted Al and Y-ion uniformly are sputtered on gamma-TiAl alloy surface with magnetically controlled sputter method, is comprised the following steps that:
(1) aluminum melting:Technical pure aluminium ingot is added in graphite crucible, is placed in 700~800 DEG C of heating environments, constant temperature insulation 30min, while remove the oxide on molten aluminum liquid surface;
(2) yttrium is melted:Yttrium block is added in feeder, then adds in graphite crucible, is placed in 700~800 DEG C of heating environments It is interior, constant temperature insulation 30min, while remove the oxide on melting yttrium liquid surface;
(3) mixed melting liquid:The aluminium liquid of molten state and yttrium liquid are poured into same graphite crucible, are stirred continuously mixed liquor, Al and Y is carried out alloying reaction, turn into alloying liquation
Alloying reaction:Al+Y→AlY;
(4) target is prepared:Mixing AlY alloy solutions are stood into 30min, will after being then gradually cooled to 680~700 DEG C Molten alloy liquid is poured into mould, pours into 100 × 3mm of Ф circular target;
(5) matrix material pre-processes:Prepare gamma-TiAl alloy, polishing, flannelette are polished to nothing and drawn step by step on abrasive paper for metallograph After the preferable burnishing surface of trace, it is placed in alcohol and is cleaned by ultrasonic;
(6) preheating, purified treatment:Al-Y alloy target materials and gamma-TiAl alloy are placed in burner hearth, regulation target and γ- Distance 15-20mm between TiAl alloy.Vacuum in burner hearth is evacuated to 10 first-4Pa, argon gas is passed through, is maintained at pressure in burner hearth 0.3-0.5Pa.Bias is imposed to Al-Y alloy target materials, processing time ensures in 10-20min, and ion is carried out to gamma-TiAl alloy Etching and cleaning, purify surface;
(7) magnetron sputtering Al-Y alloy coats:By distance controlling between Al-Y alloy target materials and gamma-TiAl alloy 15~ 25mm, in burner hearth pressure control in 0.3~0.5Pa, target power control in 150~300W, preparation time control in 3~5h, So as to obtain Al-Y alloy coats;
(8) diffusion in vacuum is annealed:Obtained Al-Y alloy coating materials are placed in vacuum atmosphere oven and carry out diffusion in vacuum Annealing, at 600~800 DEG C, soaking time is controlled in 2~3h, subsequent furnace cooling for treatment temperature control.
Mass ratio Al in wherein described Al-Y alloy target materials:Y=7:3, purity 99.99%.
The Al-Y gradients protection alloy coat prepared is placed under 650,750 and 850 DEG C of hot environments, its surfacing light It is sliding, without obvious hole, find no any wrinkling.Microstructure has massive texture, in island growth, is combined between particle Closely, extexine forms stability height, the Al of good compactness after illustrating the protection alloy coat oxidation of Al-Y gradients2O3, can be effective The interior diffusion of O atom and the external diffusion of intrinsic silicon Ti atoms are hindered, showing as Al-Y gradients protection alloy coat has well Oxidation-resistance property, finally play a part of under high temperature hostile service condition protect matrix.
Illustrate the Al-Y ladders of gamma-TiAl alloy surface refractory oxidation of the present invention below by a specific embodiment The preparation method of degree protection alloy coat.
(1) aluminum melting:Technical pure aluminium ingot is added in graphite crucible, is placed in 750 DEG C of heating environments, constant temperature insulation 30min, The oxide on molten aluminum liquid surface is removed simultaneously;
(2) yttrium is melted:Yttrium block is added in feeder, then adds in graphite crucible, is placed in 750 DEG C of heating environments, it is permanent Temperature insulation 30min, pay attention to removing the oxide on melting yttrium liquid surface;
(3) mixed melting liquid:The aluminium liquid of molten state and yttrium liquid are poured into same graphite crucible, are stirred continuously mixed liquor, Al and Y is carried out alloying reaction, turn into alloying liquation
Alloying reaction:Al+Y→AlY;
(4) target is prepared:Mixing AlY alloy solutions are stood into 30min, after being then gradually cooled to 680 DEG C, melting closed Golden liquid is poured into mould, pours into 100 × 3mm of Ф circular target;
(5) matrix material pre-processes:Prepare gamma-TiAl alloy, polishing, flannelette are polished to nothing and drawn step by step on abrasive paper for metallograph After the preferable burnishing surface of trace, it is placed in alcohol and is cleaned by ultrasonic;
(6) preheating, purified treatment:Al-Y alloy target materials and gamma-TiAl alloy are placed in burner hearth, regulation target and γ- Distance 15mm between TiAl alloy.Vacuum in burner hearth is evacuated to 10 first-4Pa, argon gas is passed through, is maintained at pressure in burner hearth 0.45Pa.Bias is imposed to Al-Y alloy target materials, processing time ensures in 10min, to gamma-TiAl alloy carry out ion(ic) etching with Cleaning, purify surface;
(7) magnetron sputtering Al-Y alloy coats:By distance controlling between Al-Y alloy target materials and gamma-TiAl alloy in 15- 20mm, in burner hearth pressure control in 0.3-0.5Pa, target power control in 150-300W, preparation time control in 3-5h, so as to Obtain Al-Y alloy coats;
(8) diffusion in vacuum is annealed:Obtained Al-Y alloy coating materials are placed in vacuum atmosphere oven and carry out diffusion in vacuum Annealing, at 700 DEG C, soaking time is controlled in 2.5h, subsequent furnace cooling for treatment temperature control.
Magnetron sputtering Al-Y alloy coat orthogonal test technological parameters and result of the test
The thickness and adhesion of alloy coat are protected according to obtained Al-Y gradients, show that the preparation technology of sample 1 is best (i.e. optimised process):Target power 150W, pressure 0.40Pa, preparation time 5h, die opening 15mm in burner hearth;
Al-Y gradients protection alloy coat is from outward appearance to inner essence followed successively by sedimentary, diffusion layer, matrix as made from optimised process The three parts such as layer;Above-mentioned sedimentary is by Al and Al3Y is formed;
As depicted in figs. 1 and 2, Al-Y gradients protection alloy coat surface is complete, fine and close as made from optimised process, microcosmic Structure is made up of block, in island growth mechanism;
As shown in Figure 3 and Figure 4, about 20 μm of sedimentary in the Al-Y gradients protection alloy coat as made from optimised process, by Al and Y compositions, about 20 μm of diffusion layer, Al and Y contents slowly decline, and Ti contents slowly rise, and feelings are mutated in the absence of constituent content Condition;
As shown in figure 5, the Al-Y gradients as made from optimised process protect alloy coat mainly by Al and Al3Y is formed, Y members It is known as and helps crystal grain thinning, so as to effectively improves the adhesion of coating and matrix;
As shown in Fig. 6, Fig. 7 and Fig. 8, the Al-Y gradients protection alloy coat as made from optimised process lives through 650 respectively, 750 and 850 DEG C of cyclic oxidation 100h's shows pattern, and surfacing is smooth, and without obvious hole, it is existing to find no any corrugation As.Microstructure has massive texture, in island growth, is tightly combined between particle, illustrates that Al-Y gradients protect alloy coat oxygen Extexine forms stability height, the Al of good compactness after change2O3, can effectively hinder the interior diffusion of O atom and intrinsic silicon Ti former The external diffusion of son, showing as Al-Y gradients protection alloy coat has good oxidation-resistance property, finally in high temperature hostile Play a part of protecting matrix under service condition.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, some improvement can also be made under the premise without departing from the principles of the invention, and these improvement also should be regarded as the present invention's Protection domain.

Claims (1)

1. a kind of preparation method of the Al-Y gradients protection alloy coat of gamma-TiAl alloy surface refractory oxidation, its feature exist In:Comprise the following steps
(1) aluminum melting:Technical pure aluminium ingot is added in graphite crucible, is placed in 700~800 DEG C of heating environments, constant temperature insulation 30min, while remove the oxide on molten aluminum liquid surface;
(2) yttrium is melted:Yttrium block is added in feeder, then adds in graphite crucible, is placed in 700~800 DEG C of heating environments, it is permanent Temperature insulation 30min, while remove the oxide on melting yttrium liquid surface;
(3) mixed melting liquid:The aluminium liquid of molten state and yttrium liquid are poured into same graphite crucible, are stirred continuously mixed liquor, makes Al Alloying reaction is carried out with Y, turns into alloying liquation
Alloying reaction:Al+Y→AlY;
(4) target is prepared:Mixing AlY alloy solutions are stood into 30min, after being then gradually cooled to 680~700 DEG C, will be melted Aluminium alloy is poured into mould, pours into 100 × 3mm of Ф circular target;
(5) matrix material pre-processes:Prepare gamma-TiAl alloy, polishing, flannelette are polished to no marking step by step on abrasive paper for metallograph After preferable burnishing surface, it is placed in alcohol and is cleaned by ultrasonic;
(6) preheating, purified treatment:Al-Y alloy target materials and gamma-TiAl alloy are placed in burner hearth, regulation target closes with γ-TiAl Distance 15-20mm between gold, vacuum in burner hearth is evacuated to 10 first-4Pa, argon gas is passed through, pressure in burner hearth is maintained at 0.3- 0.5Pa, bias is imposed to Al-Y alloy target materials, processing time ensures in 10-20min, and ion(ic) etching is carried out to gamma-TiAl alloy With cleaning, surface is purified;
(7) magnetron sputtering Al-Y alloy coats:By distance controlling between Al-Y alloy target materials and gamma-TiAl alloy 15~ 25mm, in burner hearth pressure control in 0.3~0.5Pa, target power control in 150~300W, preparation time control in 3~5h, So as to obtain Al-Y alloy coats;
(8) diffusion in vacuum is annealed:Obtained Al-Y alloy coating materials are placed in progress diffusion in vacuum annealing in vacuum atmosphere oven Processing, at 600~800 DEG C, soaking time is controlled in 2~3h, subsequent furnace cooling for treatment temperature control.
CN201510659228.6A 2015-10-12 2015-10-12 Al Y-gradients protection alloy coat of γ TiAl alloys surface refractory oxidation and preparation method thereof Expired - Fee Related CN105239049B (en)

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CN106256928B (en) * 2016-08-25 2018-09-04 常熟理工学院 Gamma-TiAl alloy surface (Al)2O3+Y2O3) AlYMoSi multilayer structure coating and preparation method thereof

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