CN105624658B - A kind of active element modified aluminide coating and its preparation technology - Google Patents
A kind of active element modified aluminide coating and its preparation technology Download PDFInfo
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- CN105624658B CN105624658B CN201410610459.3A CN201410610459A CN105624658B CN 105624658 B CN105624658 B CN 105624658B CN 201410610459 A CN201410610459 A CN 201410610459A CN 105624658 B CN105624658 B CN 105624658B
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Abstract
The invention discloses a kind of active element modified aluminide coating and its preparation technology, belong to high-temperature protection coating technical field.The coating includes β NiAl phases and active element Y, P, weight percentage, and Y is that 0.1~0.6%, P is 0.1~5%.Its preparation process is：The oxide of active element or active element and nickel are co-deposited to formation composite deposite substrate on matrix first；Then aluminising forms the modified aluminide coating containing P and Y active elements in the composite deposite substrate of deposition.Coating of the present invention has excellent anti-cyclic oxidation ability and anti-constant temperature oxidation ability.
Description
Technical field
The present invention relates to high-temperature protection coating technical field, and in particular to a kind of active element modified aluminide coating and its
Preparation technology.
Background technology
High-temperature protection coating is mainly used in the positions such as gas turbine blades, because gas turbine blades are needed to use in height
Under warm extreme condition, it is therefore desirable to which protective coating possesses excellent resistance to high temperature oxidation and heat erosion ability.And aluminide diffusion applies
Layer high temperature oxidation resistance is good, but hot corrosion resistance is poor compared with chromium compounds coating.In general aluminide diffusion is improved to apply
The resistance to high temperature oxidation and corrosion and heat resistant ability of layer are mainly started with terms of two, first, improving the combination between oxide-film and matrix
Power, second, reducing the interior diffusion of aluminium element in coating.It is contemplated that by adding the specific hand such as active element and its oxide
Section is modified to aluminide diffusion coating, to improve the adhesion between oxide-film and matrix.
The content of the invention
It is an object of the invention to provide a kind of active element modified aluminide coating and its preparation technology, is lived by P, Y
Property element coat of aluminide is modified, gained coating (>=1000 DEG C) under high temperature extreme condition, keep excellent in strength
Possess excellent resistance to high temperature oxidation and heat erosion ability while performance.
Technical solution of the present invention is as follows：
A kind of active element modified aluminide coating, the coating include β-NiAl phases and active element, the active element
For Y and P；Weight percentage, Y is that 0.1~0.6%, P is that Al content is 40 in 0.1~5%, β-NiAl phases in coating
~70%.
In the modified aluminide coating, P element is in coat of aluminide with NixP100-xForm exist, X spans
For 85~90 (atomic percents).
The modified aluminide coating layer thickness is 30-50 μm.
The preparation technology of the modified aluminide coating specifically comprises the following steps：
(1) active element (P and Y) and nickel element are co-deposited to formation composite deposite base on matrix by composite electroless-plating
Bottom；P element content is 10~17wt.% in composite deposite substrate, and Y element content is 10~20wt%, and composite deposite substrate is thick
Spend for 1~5 μm.In gained composite deposite substrate, P element is with NixP100-xForm exist, X spans are 85~90 (atoms
Percentage)；Y element is with Y2O3Form exist.
(2) Al elements are oozed by pack cementation aluminizing or low pressure gas phase deposition method in the composite deposite substrate, acquisition contains P
With the modified aluminide coating of Y active elements.
In step (1), composite electroless-plating uses nickel-phosphor bath, consisting of：NaH2PO230~40g/L, Y2O31~
5g/L, NiSO4.6H2O 30~40g/L, C6H5Na3O7.2H2O 10-20g/L, NH430~40g/L of Cl, remaining is water.It is described
Nickel-phosphor bath pH value is 8 to 10, Y2O3Granularity is 50~150 μm.
In step (1), the time of the composite electroless-plating is 30~100 minutes, and temperature is 35~50 DEG C.
In step (1), the Y2O3Activated dose of activation process before addition nickel-phosphor bath, activator is cetyl front three
The aqueous solution of base ammonium bromide, cetyl trimethylammonium bromide content is 1-5g/L in activator；The activation process time 10~30
Minute, activating treatment temperature is 60~90 DEG C.
In step (2), the powder used in pack cementation aluminizing or the low pressure gas phase deposition aluminising is iron aluminium powder and ammonium chloride
The weight ratio of mixture, ferroaluminium powder and ammonium chloride is (25~50)：1, in ferroaluminium powder iron content be 40~
50wt.%, 900~1100 DEG C of aluminising temperature, 3~5 hours aluminising time, active element penetrate into coating during aluminising and worked as
In.
The present invention has advantages below using P, Y active element modified aluminide coating compared with traditional coat of aluminide：
1st, active element modified aluminide coating of the invention for for high temperature alloy protective and preparation method thereof, Ke Yiyong
Make TBC tack coat or exclusive use.Modified aluminide diffusion coating is mainly β-NiAl, and wherein Y, P isoreactivity element are present
In coat of aluminide, active element improves the anti-cyclic oxidation ability of coating and anti-constant temperature oxidation ability.
2nd, in the case that high temperature coating forms oxide-film, Y can play a part of pinning between coating and oxide-film, suppression
Oxygenerating film comes off.
3rd, Y can suppress the generation of hole between oxide-film and coating, and P can suppress the diffusion of crystal boundary oxygen and sulphur, prevent
Internal oxidition and interior vulcanization occur for coating.
4th, due to Y and P be present among coating, in constant temperature oxidation with abnormal low oxide growth speed.
5th, excellent anti-cyclic oxidation performance.
Brief description of the drawings
Fig. 1 is sample surfaces scanning electron microscopic picture after composite electroless-plating.
Fig. 2 is the ESEM back scattering picture of sample in cross section after aluminising.
Fig. 3 be after aluminising and 200 hours constant temperature oxidations after sample surfaces xps energy spectrum.
Fig. 4 is coating in many rich yttrium oxide particles of surface appearance after 1100 DEG C of 20 1 hour cyclic oxidations；
Wherein：(a) it is sample surfaces Oxide Film Surface Appearance；(b) it is arrow meaning position power spectrum in figure (a).
Fig. 5 is several 1100 DEG C of constant temperature oxidation kinetic curves of coating.
Fig. 6 is several 1100 DEG C of cyclic oxidation kinetic curves of coating.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples.
Embodiment 1
Base material uses directional solidification nickel-base high-temperature alloy DD5, and its composition is as follows (mass percent)：Co：7.5%, Cr：
7%, W：5%, Mo：1.5%, Al：6.2%, Ta：6.5%, Re：3%, Ni：Surplus.By a diameter of 13 millimeters of high temperature alloy
Rod linear cutter cuts Φ 3mm circular hole, to facilitate plating into thick 2 millimeters disk in the top middle position of disk
Hung among the process of vapour deposition.
All samples all pass through following pretreatment before plated film：
SiC sand paper water mill is to 400#；
Wet abrasive blasting processing is carried out on sand-blasting machine, shot-peening is using 200# emergies and the mixture of glass sand, pressure
0.25MPa；
Sandblasting sample is cleaned by ultrasonic by running water, deionized water and acetone successively standby.
Prepared by yttrium P Modification aluminide diffusion coating is divided into two steps, and Composite Coatings are deposited first by composite chemical plating method
Layer substrate, then carries out aluminising by chemical vapour deposition technique, and the yttrium during aluminising in composite deposite substrate, which can turn into, oozes yttrium
Source, as aluminium element deposits to coat inside, and part P can then be burnt up by chemical vapor deposition.
Composite deposite substrate uses composite electroless plating technology, and concrete technology flow process is as follows
(1) purified treatment early stage：
Sample after sandblasting is cleaned by ultrasonic in acetone, removes the grease of coating surface, obtains fresh base
Body surface face, laid a solid foundation for coating；
(2) sensitized treatment：
Sensitized treatment formula is：
20g/l stannous chlorides, SnCl2
40ml/l concentrated hydrochloric acids, HCl
Temperature is room temperature, and sample is put into solution and is sensitized 3min；
(3) activation process：
Activation process formula is：
0.2g/l palladium bichlorides, PdCl2
2ml/l hydrochloric acid, HCl
Temperature is room temperature, time 5min；
(4) precoating：
Ni silks are put into triggering in chemical plating fluid (chemical plating needs reaction after triggering to carry out)；
(5) composite electroless-plating
Electroplate liquid formulation is：
20g/l six hydration nickel sulfates, NiSO4.6H2O
10g/l sodium citrates, C6H5Na3O7.2H2O
30g/l ammonium chlorides, NH4Cl
30g/l dibastic sodium phosphates, NaH2PO2
2.5g/l yittrium oxide, Y2O3(granularity is divided into two kinds of 50nm and 100nm, in cetyl bromination ammonium cationic table
Surface modification is carried out in the activating agent of face)
PH value is adjusted with ammoniacal liquor, scope is between 9-10,45 DEG C of bath temperature.
The plating solution preparation process of composite electroless-plating is as follows：
Weigh the nickel salt (NiSO of metering4), sodium citrate (complexing agent), NH4Cl (stabilizer), NaH2PO2(reducing agent),
Melted respectively with distilled water diluting；
Nickel salt (the NiSO that will have been dissolved4) under the conditions of (magnetic agitation) is stirred continuously, pour into complexing agent (sodium citrate)
In solution (solution is in alkalescent), nickel salt solution is formed；
Reducing agent (the NaH that will have been dissolved2PO2) solution stirring pour into stabilizer (NH4Cl (solution is in faintly acid), shape in)
Into reducing solution；
Reducing solution is poured into nickel salt solution, stirred, and it is standby to volume is calculated with distilled water diluting, obtain
Chemical plating fluid is standby；
Weigh 0.18g cetyl trimethylammonium bromides (C19H42BrN, cationic surface active agent), it is dissolved in heat
Deionized water in, 50ml solution is configured to, with the solution to Y2O3Powder is modified that (ratio is 1ml cetyl trimethyls
Ammonium bromide solution is modified 0.5gY2O3Powder), it is standby to stand 20min；
The chemical plating fluid prepared is poured into the Y activated2O3In powder beaker, it is made afterwards again using ultrasonic wave is scattered
Close the plating solution of chemical plating.
The technological parameter of composite electroless-plating is：60 minutes time, 30 DEG C of temperature.
Formation composite deposite substrate on matrix is plated in by composite chemical；P element content is in composite deposite substrate
17wt.%, Y element content are 20wt.%；Composite deposite substrate thickness is 5 μm；In gained composite deposite substrate, P element with
NixP100-xForm exist, X spans are 89 (atomic percents)；Y is with Y2O3Form exist.
Al elements are oozed by low pressure gas phase deposition method in the composite deposite substrate, composite deposite substrate during aluminising
In yttrium can turn into ooze yttrium source, as aluminium element deposits to coat inside, and part P can then be burnt up by chemical vapor deposition, most
The modified aluminide coating containing P and Y active elements is obtained eventually.
Fig. 1 is sample surfaces scanning electron microscopic picture after composite electroless-plating, as seen from the figure sample table after composite electroless-plating
Face has adhered to a large amount of white Y2O3, these Y2O3It can turn into during aluminising and ooze Y sources.
Chemical vapor deposition is carried out at 1000 DEG C, aluminising 4 hours, and powder adds ammonium chloride mixing system using iron aluminium powder
Into (ammonium chloride content 4%, powder add a small amount of NH using preceding have passed through preheating under high temperature low vacuum4Cl is pre-
Burn), argon gas is low as protective gas, vacuum.
Following reaction occurs during pack cementation aluminizing：
M(s)+AXx(l, v)=MXx(v)+A(s,v) (1)
Wherein M represents Al or Cr, A represent NH4, Y, X represent Cl.
AlClx(v)+REOy(s)=REClx(v)+AlOy(s) (2)
Wherein M represents Al or Cr, Re represent Y.
Fig. 2 is the ESEM back scattering picture of sample in cross section after aluminising, is β-NiAl in coating, thickness is about 30~
50μm。
Fig. 3 be aluminising after and 200 hours constant temperature oxidations after sample surfaces xps energy spectrum, as seen from the figure, aluminising it
Coating contains Ni afterwards89P11, it was demonstrated that P element is present among coating.
Fig. 4 is that coating surface after 1100 DEG C of 20 1 hour cyclic oxidations are passed through many rich yttrium oxide particles occurs,
Wherein：Fig. 4 (a) is sample surfaces Oxide Film Surface Appearance, the oxide that it is rich Y that arrow is signified, Fig. 4 (b) is arrow institute in Fig. 4 (a)
Refer to position power spectrum, power spectrum, which is shown in oxide, contains Y element, it was demonstrated that Y element is had penetrated among coating.
Fig. 5 is several 1100 DEG C of constant temperature oxidation kinetic curves of coating, and NiAl is to be modified without by active element in figure
Coating, Y-1 and Y-2 are yttrium P elements modified aluminide coating, difference be the Y-1 composite electroless-plating times be 30 minutes, Y-2 is multiple
It is 1 hour to close electroless plating time.From curve, yttrium P Modification coat of aluminide aoxidizes among 1100 DEG C of constant temperature oxidation processes
Weightening is few compared with coat of aluminide, illustrates its constant temperature oxidation better performances, wherein Y-2 coatings have best constant temperature oxidation performance.
Fig. 6 is several 1100 DEG C of cyclic oxidation kinetic curves of coating.Wherein NiAl, Y-1 and Y-2 are identical with Fig. 5, Ni
Coating is the high temperature alloy substrate coat of aluminide that aluminising is formed after pure Ni is electroplated, it is intended that illustrates to be previously deposited Ni elements pair
The influence of coat of aluminide.From curve, Y-1 and Y-2 coatings are weightless less under the conditions of 1100 DEG C of cyclic oxidations, especially
Y-2 coatings, still without weightlessness under the conditions of 450 hours 1100 DEG C of cyclic oxidations, there is most excellent cyclic oxidation performance.
Claims (8)
- A kind of 1. active element modified aluminide coating, it is characterised in that：The coating includes β-NiAl phases and active element, described Active element is Y and P；Weight percentage, Y is that 0.1~0.6%, P is Al in 0.1~5%, β-NiAl phases in coating Content 40~70%.
- 2. active element modified aluminide coating according to claim 1, it is characterised in that：The modified aluminide coating In, P element is in coat of aluminide with NixP100-xForm exist, X spans be 85~90.
- 3. active element modified aluminide coating according to claim 1, it is characterised in that：The modified aluminide coating Thickness is 30-50 μm.
- 4. the preparation technology of active element modified aluminide coating according to claim 1, it is characterised in that：The technique has Body comprises the following steps：(1) active element and nickel element are co-deposited to formation composite deposite substrate on matrix by composite electroless-plating；Composite Coatings P element content is 10~17wt.% in layer substrate, and Y element content is 20~30wt.%, and composite deposite substrate thickness is 1~5 μ m；(2) Al elements are oozed by pack cementation aluminizing or low pressure gas phase deposition method in the composite deposite substrate, acquisition contains P and Y The modified aluminide coating of active element.
- 5. the preparation technology of active element modified aluminide coating according to claim 4, it is characterised in that：Step (1) In the composite deposite substrate of gained, P element is with NixP100-xForm exist, X spans be 85~90；Y is with Y2O3Form In the presence of.
- 6. the preparation technology of active element modified aluminide coating according to claim 4, it is characterised in that：Step (1) In, the composite electroless-plating uses nickel-phosphor bath, consisting of：NaH2PO230~40g/L；Y2O31~5g/L；NiSO4· 6H230~40g/L of O；C6H5Na3O7·2H2O 10-20g/L；NH430~40g/L of Cl；Remaining is water；The nickel-phosphor bath pH It is worth for 8 to 10, is adjusted with ammoniacal liquor, Y2O3Granularity is 50~150 μm；The time of the composite electroless-plating is 30~100 minutes, Temperature is 35~50 DEG C.
- 7. the preparation technology of active element modified aluminide coating according to claim 6, it is characterised in that：Step (1) In, the Y2O3Activated dose of activation process before addition nickel-phosphor bath, activator are water-soluble for cetyl trimethylammonium bromide Liquid, its concentration are 1-5g/L；10~30 minutes activation process time, activating treatment temperature are 60~90 DEG C.
- 8. the preparation technology of active element modified aluminide coating according to claim 4, it is characterised in that：Step (2) In, the powder that the pack cementation aluminizing or low pressure gas phase deposition use is ferroaluminium powder and the mixture of ammonium chloride, ferroaluminium The weight of powder and ammonium chloride ratio is (25~50)：1, iron content is 40~50wt.% in ferroaluminium powder；Aluminising temperature 900~1100 DEG C, 3~5 hours aluminising time, active element is penetrated among coating during aluminising.
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| CN108642535B (en) * | 2018-05-31 | 2019-09-06 | 上海工程技术大学 | A kind of preparation method of ceria modified aluminide gradient coating system |
| CN108660412B (en) * | 2018-06-14 | 2019-07-16 | 沈阳梅特科航空科技有限公司 | Modified β-NiAl coating of a kind of active element and preparation method thereof and workpiece |
| CN110295383B (en) * | 2019-07-19 | 2021-04-13 | 中国科学院金属研究所 | Cr modified aluminide coating and preparation method thereof |
| CN111850529B (en) * | 2020-07-30 | 2022-07-08 | 西安热工研究院有限公司 | Anti-oxidation coating for high-temperature steam valve bolt of generator set and preparation method of anti-oxidation coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066690A (en) * | 1991-05-13 | 1992-12-02 | 中国科学院金属腐蚀与防护研究所 | High-temperature corrosion resistant coating and preparation process thereof |
| CN1280210A (en) * | 1999-06-08 | 2001-01-17 | Abb阿尔斯托姆电力(瑞士)股份有限公司 | Beta Phase containing nickel-aluminium coating |
| EP1541714A1 (en) * | 2003-11-13 | 2005-06-15 | General Electric Company | Method for repairing components using environmental bond coatings and resultant repaired components |
-
2014
- 2014-10-31 CN CN201410610459.3A patent/CN105624658B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066690A (en) * | 1991-05-13 | 1992-12-02 | 中国科学院金属腐蚀与防护研究所 | High-temperature corrosion resistant coating and preparation process thereof |
| CN1280210A (en) * | 1999-06-08 | 2001-01-17 | Abb阿尔斯托姆电力(瑞士)股份有限公司 | Beta Phase containing nickel-aluminium coating |
| EP1541714A1 (en) * | 2003-11-13 | 2005-06-15 | General Electric Company | Method for repairing components using environmental bond coatings and resultant repaired components |
Non-Patent Citations (2)
| Title |
|---|
| Cyclic oxidation of β-NiAl with various reactive element dopants at 1200℃;Dongqing Li etal.;《Corrosion Science》;20120919;第66卷;第125-135页 * |
| 稀土及稀土氧化物改性的铝化物涂层;王福会;《材料保护》;19931031;第16卷(第5期);第4-7页 * |
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Effective date of registration: 20220523 Address after: Room 779, No. 155-5 Innovation Road, Dongling District, Shenyang City, Liaoning Province, 110000 Patentee after: SHENYANG MEITEKE AVIATION TECHNOLOGY Co.,Ltd. Address before: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee before: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES |
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