CN105624522A - Single-phase platinum modified aluminide coating and preparation process thereof - Google Patents
Single-phase platinum modified aluminide coating and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a single-phase platinum modified aluminide coating and a preparation process thereof and belongs to the technical field of high-temperature protective coatings. Firstly, platinum is deposited on a matrix to form a platinum plating substrate layer; then, an element Al is deposited on the platinum plating substrate layer; and finally, the single-phase platinum modified aluminide coating is obtained. The single-phase platinum modified aluminide coating is a beta-(Ni and Pt) Al single-phase coating. The coating comprises 30wt%-40wt% of the element Al, 20wt%-30wt% of the element Pt and 30wt%-40wt% of element Ni. According to the single-phase platinum modified aluminide coating and the preparation process thereof, the aluminide diffusion coating has only a beta-(Ni and Pt) Al phase, and the element Pt exists in a beta-NiAl phase; the single beta-NiAl coating does not comprise a PtAl2 phase, so the TBC cyclic oxidation resistance lifetime at a high temperature can be prolonged.
Description
Technical field
The present invention relates to high-temperature protection coating technical field, be specifically related to a kind of single-phase platinum modified aluminide coating and preparation technology thereof.
Background technology
As a kind of platinum modified aluminide coating with good antioxidation, hot corrosion resistance, it is widely used in the protection of the heat-resistant part such as aero-engine, gas turbine blades, it both can be used alone, it is also possible to as adhesive linkage (bondcoat) with ceramic layer on surface (such as Y2O3Stablize ZrO2) constitute thermal barrier coating (TBCs, i.e. thermalbarriercoatings) system together, improve the resistance to high temperature oxidation of parts, hot corrosion resistance, the service life of elongate member. The document of related application such as 1. Chinese invention patent, ��-NiAl thermal barrier coating that Pt+Si is modified and preparation method thereof, application number 201210078703.7; 2. Chinese invention patent, for the NiCoCrAlY modified through platinum of heat insulating coat in conjunction with coating, application number 200610169095.5; 3. Chinese invention patent, a kind of protective coating, application number 200410003852.2 etc.
For high temperature alloy and high-temperature protection coating parts, its antioxygenic property relies primarily on: (1) one layer of fine and close and poky Al2O3Film, stops the interior external diffusion of element; (2) yttria-stabilized zirconia ceramic coating reduces the temperature of tie layer surface. But due to Al2O3Film and ceramic coating are very crisp, and the fold that tack coat coating in use surface occurs rises and falls and easilys lead to Al2O3Film and ceramic coating come off, and therefore suppress tack coat surface folding in pyroprocess can improve the service life of TBCs coating.
In platinum modified aluminide coating, common intermetallic compound has ��-(Ni, Pt) Al, �� '-(Ni, Pt)3Al and PtAl2Deng, �� '-(Ni, Pt)3In Al, Al content is too low and can not maintain for a long time and generate single Al2O3Film, and PtAl2Too crisp, it is easy to peel off, and structural instability, it is easy to being changed into ��-(Ni, Pt) Al in high-temperature oxidation process, phase transformation causes coating change in volume thus causing surface folding, ultimately results in Al2O3Film and ceramic coating come off. And ��-(Ni, Pt) Al is that desirable coating exists phase, it has stable structure and higher Pt, Al solid solubility, it is suitable as the articulamentum of TBCs system, therefore ��-(Ni, Pt) the Al coating how preparing single-phase becomes the key extending high-temperature protection coating active time.
Summary of the invention
In order to extend the active time of TBCs thermal barrier coating, it is an object of the invention to provide a kind of single-phase platinum modified aluminide coating and preparation technology thereof. Coating of the present invention contains only stable ��-(Ni, Pt) Al homogeneous structure, while ensureing coating heat stability, provides aluminum and the platinum element of enough content. Therefore it is possible to prevent the coating surface fold owing to phase transformation change in volume causes, improves the service life of the coating of TBCs thermal boundary.
To achieve these goals, the technical scheme is that
A kind of single-phase platinum modified aluminide coating, this coating is ��-(Ni, Pt) the single-phase coating of Al, Pt, Al and Ni element is at ��-(Ni, Pt) Al phase is uniformly distributed, wherein: Al constituent content is 30-40wt%, Pt constituent content be 20-30wt%, Ni constituent content is 30-40wt%.
Described single-phase platinum modified aluminide coating preparation process is: first at substrate deposit platinum element to form platinized substrate, then depositing Al element on described platinized substrate, the single-phase platinum modified aluminide coating of final acquisition; Specifically include following steps:
(1) by plating, Pt is deposited on matrix and forms platinized substrate; The thickness of described platinized substrate is 1-15 ��m.
(2) formed single-phase containing ��-(Ni, Pt) Al at platinized substrate Al deposited above element or contain ��-(Ni, Pt) Al and PtAl2The coating of two-phase, the PtAl in two-phase coating2After being eliminated by heat treatment, form the single-phase coating containing only ��-(Ni, Pt) Al.
In step (1), the plating solution that described electroplating technology adopts consists of: platinum content is the dinitroso diammonia platinum ((NH of 6-10g/L3)2Pt(NO2)2), the sulfamic acid (NH of 20-65g/L2SO3H), the dodecyl dimethyl additive of 1g/L, all the other are water; Bath pH value is 1-5, and bath temperature is 60-90 DEG C, and electroplating current density is 1-10A/dm2, electroplating time is arrive 2h in 10 minutes.
After step (1) gained platinized substrate is carried out heat treatment, then carry out step (2); Described heat treatment temperature is 1000-1100 DEG C, and heat treatment time is 1-3 hour. After heat treatment, platinized substrate is �� (Ni, Pt) and �� ' (Ni, Pt)3Al; In platinized substrate after heat treatment, Pt content is 85-95wt%, Ni content be 10-20wt%, Al content is 1-10wt%.
In step (2), the deposition of aluminium element adopts pressed powder embedding techniques or low vacuum vapor deposition technology; In pressed powder embedding techniques, platinized substrate is embedded in pressed powder, and in low vacuum vapor deposition technology, platinized substrate is suspended on pressed powder. Described pressed powder includes inert agents, activator and aluminising source, and wherein: inert agents is 0-50wt%, activator is 1-6wt%, aluminising source surplus; Described inert agents is alumina powder, and activator is ammonium chloride, and aluminising source is ferroaluminium powder.
In step (2), in the deposition process of aluminium element (aluminising), temperature 900-1100 DEG C, 3-6 hour time; Aluminising is subsequently formed the coating containing only ��-single-phase for (Ni, Pt) Al, or is formed containing ��-(Ni, Pt) Al and PtAl2The coating of two-phase.
The thermally treated acquisition of two-phase coating formed after aluminising contains only the described single-phase platinum modified aluminide coating of ��-(Ni, Pt) Al single-phase; Heat treatment temperature 1000-1200 DEG C, heat treatment time 1-4 hour; Or, heat treatment temperature 800-900 DEG C, heat treatment time 15-25 hour.
The present invention single-phase platinum modified aluminide coating contains PtAl with traditional2Coating is compared and is had the advantage that
1. the present invention is by electroplating the method being combined with Diffusional aluminizing, prepares single-phase platinum modified aluminide coating, contains only ��-(Ni in coating, Pt) Al is single-phase, platinum aluminum nickel element is uniformly distributed in ��-(Ni, Pt) Al phase, without PtAl in coating2Phase, due to PtAl2Comparing crisp, can be transformed into ��-NiAl phase in applied at elevated temperature process, the change in volume that its phase transformation causes can cause surface folding to cause coming off of TBC, and does not contain PtAl in the present invention single-phase ��-NiAl coating2Phase, therefore can improve the anti-cyclic oxidation life-span of TBC under high temperature.
2. coating toughness of the present invention relatively contains PtAl2Coating to be got well.
3. �� of the present invention-(Ni, Pt) Al Stability Analysis of Structures, platinum element and aluminium element solubility range wherein is wider, is not susceptible to phase transformation.
4. fusing point of the present invention is higher, it is provided that enough aluminium elements form Al2O3Film, high temperature resistant property is good.
5. platinum layer deposition velocity of the present invention is fast, within 1 hour, can deposit more than 10 ��m.
6. coating of the present invention can serve as the bonding coat of TBC.
Accompanying drawing explanation
Fig. 1 is that after embodiment 2 electroplates 10min, 20min and 40min respectively, gained platinized substrate XRD figure after the heat treatment is composed; In figure: (a) electroplates 10min; (b) plating 20min; (c) plating 40min.
Fig. 2 is that after embodiment 2 electroplates 10min, 20min and 40min respectively, gained platinized substrate is composed then through the XRD figure after heat treatment and aluminising; In figure: (a) electroplates 10min; (b) plating 20min; (c) plating 40min.
Fig. 3 is that after embodiment 2 electroplates 10min, 20min and 40min respectively, gained platinized substrate in aluminising and has carried out the XRD figure spectrum after after-baking.
Fig. 4 is a part for 1100 DEG C of Ni-Al-Pt phasors, the figure illustrates the embodiment of the single-phase �� of the present invention-(Ni, Pt) Al alloy compositions.
Fig. 5 is the sectional view of ��-single-phase coating of (Ni, Pt) Al in display DD5 high temperature alloy substrate.
Fig. 6 has two-phase ��-(Ni, Pt) Al and PtAl2Cyclic oxidation performance comparison figure with single-phase ��-(Ni, Pt) Al.
Detailed description of the invention
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
Base material adopts directional solidification nickel-base high-temperature alloy DD5,
Its chemical composition following (mass percent): Co:7.5%, Cr:7%, W:5%, Mo:1.5%, Al:6.2%, Ta:6.5%, Re:3%, Ni: surplus. The high temperature alloy rod linear cutter that diameter is 13 millimeters becomes the disk of thick 2 millimeters, and above disk, the circular hole of �� 3mm is cut in position, middle, hangs to facilitate in the plating process with vapour deposition.
Use dinitroso diammonia platinum (Pt (NH3)4(OH)2) prepare electroplate liquid, plating solution contains: the dinitroso diammonia platinum (this concentration is to calculate by the platinum content in plating solution) of 10g/L, the sulfamic acid (NH of 65g/L2SO3H), 1g/L dodecyl dimethyl additive, all the other are water;
High temperature alloy matrix sample is milled to #400 grit finish by SiC paper, next cleans with the following step. First by sample sandblasting in the sandblasting machine that pressure is 0.3MPa. Then sample is dried up successively in clear water-deionization boiling standby after ultrasonic cleaning. Then this sample is immersed in wang aqueous solution 30 seconds, is then immersed in distilled water.
Next the sample prepared is electroplated immediately. Condition is as follows:
Electric current density=10A/dm2
Temperature=90 DEG C
PH=2 (uses sulfamic acid NH2SO3H regulates)
Sedimentation time=30 minute
Distance=3cm between anode and negative electrode
Anode: platinum
Anode: surface area ratio=2 of negative electrode
Aluminising adopts low vacuum vapor deposition, and the aluminising source of employing is ferroaluminium powder, inertialess agent, and activating agent is ammonium chloride. Wherein ammonium chloride is the 4% of total aluminizing medium weight. Being hung on by sample on powder, under vacuum conditions aluminising 6 hours, temperature is 1000 DEG C, and heating rate is 6 DEG C/min. After aluminising, the sectional view of gained coating (Pt-1 coating) is as shown in Figure 5, analyzed by EDS and draw, average platinum content in coating is that 28wt.%, XRD interpretation of result coat inside is organized as ��-(Ni, Pt) Al homogeneous structure (Fig. 4).
Embodiment 2
Matrix alloy adopts DD5 high temperature alloy equally, and the high temperature alloy rod linear cutter that diameter is 13 millimeters becomes the disk of thick 2 millimeters, and above disk, the circular hole of �� 3mm is cut in position, middle, hangs to facilitate in the plating process with vapour deposition.
Use dinitroso diammonia platinum (Pt (NH3)4(OH)2) prepare electroplate liquid. Plating solution contains: platinum content is the dinitroso diammonia platinum ((NH of 6g/L3)2Pt(NO2)2), the sulfamic acid (NH of 25g/L2SO3H), all the other are water;
High temperature alloy substrate sample is milled to #400 grit finish by SiC paper, cleans with the following step afterwards. First by sample sandblasting in the sandblasting machine that pressure is 0.3Mpa. Then by sample successively in clear water-deionization boiling ultrasonic cleaning standby with drying up. Before plating, sample is through electrolytic degreasing (5wt% sodium hydrate aqueous solution, electric current density 10A/dm2, room temperature 30 seconds) and (Nickel dichloride. adds hydrochloric acid plating solution, electric current 4A/dm to-nickel preplating in-activation (chloroazotic acid activates 30 seconds)2, room temperature preplating 30s) and-deionized water five steps of cleaning.
Next the sample prepared is electroplated immediately. Condition is as follows:
Electric current density=3A/dm2
Temperature=70 DEG C
PH=1 (uses sulfamic acid NH2SO3H regulates)
Sedimentation time is 10 minutes (Pt-1.5) respectively, 20 minutes (Pt-2), 40 minutes (Pt-4)
Distance=5cm between anode and negative electrode
Anode: platinum
Anode: surface area ratio=4 of negative electrode
Deposition different time gained platinized substrate layer thickness is respectively as follows: Pt-1.5:1 ��m (10min), Pt-2:2 ��m (20min), Pt-4:4 ��m (40min). The platinized substrate prepared removes hydrogen in 2 hours at 260 DEG C of heat treatments, within 3 hours, improves the toughness of platinum layer at 400 DEG C of heat treatments, it is prevented that cracking. Last in the counterdiffusion in 1 hour of 1100 DEG C of heat treatments, the XRD figure of platinized substrate after heat treatment is composed as shown in Figure 1, it can be seen that after diffusion, platinum layer surface forms ��-(Ni, Pt) and �� '-(Ni, Pt)3Al phase, �� '-(Ni, Pt)3The platinum element that is formed as of Al reduces the activity of matrix surface aluminium element, and aluminium element outwards diffuses to form �� '-(Ni, Pt)3Al��
Aluminising adopts low vacuum vapor deposition technology, and the aluminising source of employing is ferroaluminium powder, and inert agents is aluminium oxide, and activating agent is ammonium chloride. Wherein ferroaluminium powder and alumina weight are than for 1:1, and ammonium chloride is the 2% of gross weight. Being hung on by sample on powder, under vacuum conditions aluminising 6 hours, temperature is 1040 DEG C, and heating rate is 6 DEG C/min.
Fig. 2 is XRD figure analysis of spectrum structure (Pt-1.5, Pt-2, Pt-4) of sample after aluminising, defines ��-(Ni, Pt) Al and PtAl at coating surface2Duplex structure.
Fig. 3 is XRD figure analysis of spectrum structure (Pt-1.5post, Pt-2post, Pt-4post) after heat treatment, and technique is 1100 DEG C of heat treatments 4 hours, then 900 DEG C of heat treatments 16 hours. Fig. 3 analyzes result and shows after heat treatment ��-(Ni, Pt) Al and PtAl in coating2Duplex structure (Pt-1.5, Pt-2 and Pt-4) becomes single-phase ��-(Ni, Pt) Al and organizes (Pt-1.5post, Pt-2post, Pt-4post).
Fig. 6 is single-phase ��-(Ni, Pt) Al coating and ��-(Ni, Pt) Al and PtAl2Two-phase coating and 1150 DEG C of cyclic oxidation dynamic curves of common coat of aluminide, wherein Pt-1 is the single-phase ��-(Ni in embodiment 1, Pt) Al coating, Pt-2 and Pt-4 is ��-(Ni, Pt) Al and the PtAl in embodiment 2 without annealing2Two-phase coating, Pt-2post and Pt-4post be annealed in embodiment 2 after single-phase ��-(Ni, Pt) Al coating, NiAl is common coat of aluminide.
In figure visible, Pt-1 and the Pt-2post initial stage form oxide-film after kinetic curve become steady, illustrate that it has low oxide growth speed, and weightlessness do not occur, and namely common NiAl occurs in that obvious weightlessness for 40 hours at 1150 DEG C, illustrate that oxide-film has begun to peel off. And Pt-2 is constantly in weightening finish state, Pt-4 coating also occurred slight weightless after 110 hours, and in sum, in embodiment 1, in Pt-1 and embodiment 2, the single-phase �� of Pt-2post-(Ni, Pt) Al coating has best anti-cyclic oxidation performance.
Claims (10)
1. a single-phase platinum modified aluminide coating, it is characterised in that: this coating is ��-single-phase coating of (Ni, Pt) Al, and in coating, Al constituent content is 30-40wt%, Pt constituent content be 20-30wt%, Ni constituent content is 30-40wt%.
2. the preparation technology of single-phase platinum modified aluminide coating according to claim 1, it is characterized in that: this technique first at substrate deposit platinum element to form platinized substrate, then depositing Al element on described platinized substrate, the single-phase platinum modified aluminide coating of final acquisition; Specifically include following steps:
(1) by plating, Pt is deposited platinum element on matrix, form platinized substrate;
(2) formed single-phase containing ��-(Ni, Pt) Al at platinized substrate Al deposited above element or contain ��-(Ni, Pt) Al and PtAl2The coating of two-phase, the PtAl in two-phase coating2After being eliminated by heat treatment, form the single-phase coating containing only ��-(Ni, Pt) Al.
3. the preparation technology of single-phase platinum modified aluminide coating according to claim 2, it is characterized in that: in step (1), the plating solution that described electroplating technology adopts consists of: platinum content is the dinitroso diammonia platinum of 6-10g/L, the sulfamic acid of 20-65g/L, 0.1g/L dodecyl dimethyl additive, all the other are water; Bath pH value is 1-5, and bath temperature is 60-90 DEG C, and electroplating current density is 1-10A/dm2, electroplating time is 10 minutes to 2 hours.
4. the preparation technology of single-phase platinum modified aluminide coating according to claim 2, it is characterised in that: the thickness of described platinized substrate is 1-15 ��m.
5. the preparation technology of single-phase platinum modified aluminide coating according to claim 2, it is characterised in that: after step (1) gained platinized substrate is carried out heat treatment, then carry out step (2); Described heat treatment temperature is 1000-1100 DEG C, and heat treatment time is 1-3 hour.
6. the preparation technology of single-phase platinum modified aluminide coating according to claim 5, it is characterised in that: after heat treatment, platinized substrate is �� (Ni, Pt) and �� ' (Ni, Pt)3Al; In platinized substrate after heat treatment, Pt content is 85-95wt%, Ni content be 10-20wt%, Al content is 1-10wt%.
7. the preparation technology of single-phase platinum modified aluminide coating according to claim 2, it is characterised in that: in step (2), the deposition of aluminium element adopts pressed powder embedding techniques or low vacuum vapor deposition technology; In pressed powder embedding techniques, platinized substrate is embedded in pressed powder, and in low vacuum vapor deposition technology, platinized substrate is suspended on pressed powder.
8. the preparation technology of single-phase platinum modified aluminide coating according to claim 7, it is characterised in that: described pressed powder includes inert agents, activator and aluminising source, and wherein: inert agents is 0-50wt%, activator is 1-6wt%, aluminising source surplus; Described inert agents is alumina powder, and activator is ammonium chloride, and aluminising source is ferroaluminium powder.
9. the preparation technology of single-phase platinum modified aluminide coating according to claim 7, it is characterised in that: in the deposition process of aluminium element, temperature 900-1100 DEG C, 3-6 hour time; Deposition is subsequently formed the coating containing only ��-single-phase for (Ni, Pt) Al, or is formed containing ��-(Ni, Pt) Al and PtAl2The coating of two-phase.
10. the preparation technology of single-phase platinum modified aluminide coating according to claim 9, it is characterized in that: the thermally treated acquisition of coating formed after aluminium element deposition contains only the described single-phase platinum modified aluminide coating of ��-(Ni, Pt) Al single-phase; Heat treatment temperature 1000-1200 DEG C, heat treatment time 1-4 hour; Or, heat treatment temperature 800-900 DEG C, heat treatment time 15-25 hour.
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Cited By (6)
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| CN107268044A (en) * | 2017-05-22 | 2017-10-20 | 中国科学院金属研究所 | A kind of Pt Zr modified aluminide coating productions |
| CN108660412A (en) * | 2018-06-14 | 2018-10-16 | 沈阳梅特科航空科技有限公司 | β-NiAl coatings that a kind of active element is modified and preparation method thereof and workpiece |
| CN112064072A (en) * | 2020-08-28 | 2020-12-11 | 中国科学院金属研究所 | Method for preparing single-phase Pt-Al coating on surface of nickel-based single-crystal superalloy |
| CN112301389A (en) * | 2020-10-29 | 2021-02-02 | 中国航发南方工业有限公司 | Method for preparing platinum-aluminum coating |
| CN113512702A (en) * | 2021-07-14 | 2021-10-19 | 北航（四川）西部国际创新港科技有限公司 | Single-phase beta-NiAl bonding layer and preparation method thereof |
| CN115558892A (en) * | 2022-10-14 | 2023-01-03 | 上海奥莱雅康医疗科技有限公司 | Coating containing platinum |
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| CN107268044A (en) * | 2017-05-22 | 2017-10-20 | 中国科学院金属研究所 | A kind of Pt Zr modified aluminide coating productions |
| CN108660412A (en) * | 2018-06-14 | 2018-10-16 | 沈阳梅特科航空科技有限公司 | β-NiAl coatings that a kind of active element is modified and preparation method thereof and workpiece |
| CN112064072A (en) * | 2020-08-28 | 2020-12-11 | 中国科学院金属研究所 | Method for preparing single-phase Pt-Al coating on surface of nickel-based single-crystal superalloy |
| CN112301389A (en) * | 2020-10-29 | 2021-02-02 | 中国航发南方工业有限公司 | Method for preparing platinum-aluminum coating |
| CN112301389B (en) * | 2020-10-29 | 2022-04-15 | 中国航发南方工业有限公司 | Method for preparing platinum-aluminum coating |
| CN113512702A (en) * | 2021-07-14 | 2021-10-19 | 北航（四川）西部国际创新港科技有限公司 | Single-phase beta-NiAl bonding layer and preparation method thereof |
| CN113512702B (en) * | 2021-07-14 | 2023-02-28 | 北航（四川）西部国际创新港科技有限公司 | Single-phase beta-NiAl bonding layer and preparation method thereof |
| CN115558892A (en) * | 2022-10-14 | 2023-01-03 | 上海奥莱雅康医疗科技有限公司 | Coating containing platinum |
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