CN108660412A - β-NiAl coatings that a kind of active element is modified and preparation method thereof and workpiece - Google Patents
β-NiAl coatings that a kind of active element is modified and preparation method thereof and workpiece Download PDFInfo
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- CN108660412A CN108660412A CN201810627047.9A CN201810627047A CN108660412A CN 108660412 A CN108660412 A CN 108660412A CN 201810627047 A CN201810627047 A CN 201810627047A CN 108660412 A CN108660412 A CN 108660412A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/06—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases
- C23C10/14—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases more than one element being diffused in one step
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/04—Diffusion into selected surface areas, e.g. using masks
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Vapour Deposition (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
β NiAl coatings being modified the invention discloses a kind of active element and preparation method thereof and workpiece.With the total weight of β NiAl coatings, which includes 15 40wt% of Al elements, active element 1 10wt%, surplus Ni.Halide gas is deposited to form coating by the present invention using chemical vapor deposition method in work piece inner surface, and there is no the risks of obstruction cooling duct；Coating forms oxidation film under high temperature, extends service life, has very excellent anti-cyclic oxidation performance；The β NiAl coating structures of the present invention are stablized, and solubility range is wider wherein for aluminium element, is not susceptible to phase transformation；The binding force of coating and matrix can be improved in Si, Co or Cr element that the present invention uses.
Description
Technical field
The invention belongs to high-temperature protection coating technical field, the β-NiAl being modified more particularly, to a kind of active element
Coating and preparation method thereof and workpiece.
Background technology
High-temperature protection coating is mainly used in the positions such as gas turbine blades, since gas turbine blades are needed in high temperature pole
It is used under the conditions of end, it is therefore desirable to which protective coating has excellent resistance to high temperature oxidation and heat erosion ability.Due to gas turbine into
The continuous improvement of gas port temperature needs advanced air film cooling technology to reduce the temperature in use of the thermal parts such as blade, therefore blade
Be designed as complicated hollow-core construction, internal cooling channel also needs to be protected more.Common means of defence have investment,
There is the risk of obstruction cooling duct in three kinds of slurry process and vapor deposition, investment and slurry process, vapor deposition is to be most suitable for
The method that labyrinth cooling duct deposits protective coating.Modified aluminide diffusion coating high temperature oxidation resistance and corrosion and heat resistant
Ability is good.In general it improves the resistance to high temperature oxidation of aluminide diffusion coating and corrosion and heat resistant ability mainly enters in terms of two
Hand, first, the binding force between oxidation film and matrix is improved, second is that reducing the interior diffusion of aluminium element in coating.Specific means packet
Addition Si elements or Co elements or Cr elements and its oxide are included to be modified to aluminum coating, to improve oxidation film and matrix
Between binding force.
Chinese invention patent application CN 201210078703.7 disclose Pt+Si modification β-NiAl thermal barrier coatings and its
Preparation method, the thermal barrier coating is using nickel base superalloy as basis material, by the way that one layer of platinum is electroplated in matrix surface, then in height
The lower heat treatment of temperature reaches the modification to coating；By the aluminising of investment substep and siliconising, modified coating is prepared；Using vacuum
Encapsulation technology carries out high-temperature heat treatment to coating, prepares coating in homogeneous thickness；Using plasma spraying method in Ni-based height
Temperature alloy surface spraying deposits one layer of 7~8%Y2O3Stable ZrO2Ceramics.The coating prepared has good inoxidizability
Energy and adhesive property, can extend the service life of high temperature alloy.
Chinese invention patent application CN 200610169095.5, which discloses a kind of turbine engine components, to be had by Ni-based super
The NICOCRALY combination coatings being modified through platinum of the substrate and application that alloy is formed on the surface of the substrate.Two kinds are described to be used for
The method for forming the NICOCRALY combination coatings being modified through platinum.
Chinese invention patent application CN 200410003852.2 discloses a kind of protective coating, be made of following element (with
Weight percent meter)：The reactive rare earth of at least one of the nickel of 26-30%, the chromium of 20-28%, the aluminium of 8-12%, 0.1-3%
Element, the cobalt of surplus.
The problem of above prior art is total mainly has：Of high cost, preparation method is complicated, and resistance to high temperature oxidation and heat
Corrosive nature is not strong, and the service life of component falls short of.
Invention content
The present invention be directed to problem above of the existing technology, and it is an object of the present invention to provide it is a kind of it is at low cost, preparation method is simple,
Anti- cyclic oxidation ability and the strong β-NiAl coatings of oxidation-resistance property, increase the binding force of coating and matrix, reduce calorize
The interior diffusion of aluminium element in object coating.
To achieve the goals above, the first aspect of the present invention provides a kind of β-NiAl coatings that active element is modified, with
The total weight of β-NiAl coatings, the β-NiAl coatings include Al element 15-40wt%, active element 1-10wt%, and surplus is
Ni。
According to the present invention, the active element is solid-solution in β-NiAl coatings or exists in the form of precipitated phase.
The active element that those skilled in the art routinely use may be used in the active element, it is preferable that the activity
Element is selected from least one of Si, Co and Cr.
The second aspect of the present invention provides the preparation method of the β-NiAl coatings, which includes：
Work piece inner surface channel is connected in the tooling equipped with aluminising source, heating, heat preservation, in the protection of inert gas
Under, the nickel in workpiece diffuses to work piece inner surface from inside to outside, the aluminising source chemical vapor deposition in tooling to work piece inner surface,
Form the β-NiAl coatings that active element is modified, wherein the workpiece is nickel base superalloy material；
Preferably, workpiece is placed in falcon tooth tooling, ensures that work piece inner surface way vent is smooth, work piece inner surface is led to
Road is connected in the tooling equipped with aluminising source and fixed, then heating, heat preservation.
Contain the halide of active element and the halide of Al in the aluminising source；
The aluminising source by 0.1-3wt% the metal powder of active element, the aluminum fluoride of 0.1-1wt%, 0.05-
The ferroaluminium powder of the ammonium chloride of 0.5wt%, surplus is obtained by the reaction at 900-1100 DEG C, and each weight percent is with reactant
On the basis of total weight.
When active element is Si and/or Co and/or Cr, the principle of reaction that may be present in the forming process of aluminising source
For：
1)AlF3·3H2O==AlF3+3H2O
2)2Al+AlF3==3AlF
3)2AlF3+3H2O==Al2O3+6HF
4) Si+4HF==SiF4(gas)+2H2(gas)
5)Co+2NH4Cl==CoCl2+2NH3(gas)+H2(gas)
6)Cr+2NH4Cl==CrCl2+NH3(gas)+H2(gas)
As the preferred embodiment of the present invention, the inert gas is argon gas.
As the preferred embodiment of the present invention, the thickness of obtained β-NiAl coatings is 15-70 μm, preferably 20-30 μ
m。
As the preferred embodiment of the present invention, the ventilatory capacity of inert gas is (1-20L/min)/workpiece.
As the preferred embodiment of the present invention, the time of chemical vapor deposition is 1-6h, preferably 2-5h, chemical gaseous phase
The temperature of deposition is 900-1100 DEG C, and more preferably 1000-1080 DEG C, at this temperature, chemical vapor deposition is better excellent
It is different.
As the preferred embodiment of the present invention, the preparation method includes the pre-treatment step of workpiece, the workpiece
Pre-treatment step is：Workpiece is cleaned after dry blasting is handled.
As the preferred embodiment of the present invention, the shot-peening that dry blasting uses when handling is done for emergy and/or glass sand
The pressure of blasting treatment is 0.4-0.8MPa.
The third aspect of the present invention provides a kind of tool cated workpiece, the coating be the β-NiAl coatings and/
Or coating made from the preparation method.
Beneficial effects of the present invention：
(1) halide gas is deposited to form coating by the present invention using chemical vapor deposition method in work piece inner surface, no
In the presence of the risk of obstruction cooling duct；
(2) coating forms oxidation film under high temperature, extends service life, has very excellent anti-cyclic oxidation performance；
(3) β-NiAl coating structures of the invention are stablized, and solubility range is wider wherein for aluminium element, is not susceptible to phase
Become；
(4) fusing point of the present invention is higher, can provide enough aluminium elements and form Al2O3Film, high temperature resistant property are good；
(5) binding force of coating and matrix can be improved in Si, Co or the Cr element that the present invention uses.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 shows the section metallograph of work piece inner surface depositing Al Si coatings in the embodiment of the present invention 1；
Fig. 2 shows the section metallographs of work piece inner surface depositing Al Co coatings in the embodiment of the present invention 2；
Fig. 3 shows work piece inner surface Si modification coat of aluminide EDS analysis results in the embodiment of the present invention 1；
Fig. 4 shows the EDS analysis results of the cobalt improved coat of aluminide of work piece inner surface in the embodiment of the present invention 1；
Fig. 5 shows work piece inner surface coating Preparation equipment of the present invention；
Fig. 6 shows at 1000 DEG C of coating made from the embodiment of the present invention 1 coating cross sections SEM shapes after 30 thermal shock tests
Looks.
Specific implementation mode
The preferred embodiment of the present invention is described in more detail below.Although the following describe the preferred implementations of the present invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without should be limited by embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
Embodiment 1
Workpiece is pre-processed, the pretreated step includes：Workpiece is subjected to dry blasting processing on sand-blasting machine,
Shot-peening uses the mixture of 120# emergies and glass sand, pressure 0.6MPa；It is clear by deionized water ultrasound to sandblasting sample
It washes spare.
Pretreated workpiece is placed in falcon tooth tooling, ensures that work piece inner surface way vent is smooth, by table in workpiece
Face channel is connected in the tooling equipped with aluminising source and fixes, under protection of argon gas (ventilatory capacity is (4L/min)/workpiece), adds
Heat keeps the temperature 1.5h to 920 DEG C, 10 DEG C/min of heating rate, and the nickel in workpiece diffuses to work piece inner surface from inside to outside, in tooling
Aluminising source chemical vapor deposition to work piece inner surface, form the β-NiAl coatings that active element is modified；With β-NiAl coatings
Total weight, the β-NiAl coatings include Al elements 30wt%, Si element 2.5wt%, surplus Ni.
Wherein, the workpiece is directional solidification nickel-base high-temperature alloy DD5 materials, and ingredient is following (mass percent)：Co：
7.5, Cr：7, W：5, Mo：1.5, Al：6.2, Ta：6.5, Re：3, Ni：Surplus.
The aluminising source is existed by the ferroaluminium powder of the aluminum fluoride of 100g, the ammonium chloride of 50g, the silica flour of 500g, 19.35kg
It is obtained by the reaction at 920 DEG C, obtains the β-NiAl coatings of Si modification.
Principle is：
Si+4HF==SiF4(gas)+2H2(gas),
The inner surface section metallograph that sample is made is as shown in Figure 1；As it can be seen that β-NiAl coating cross sections metallographs in figure,
Aluminium silicon coating surfacing, thickness overall distribution are uniform.
The inner surface section XPS analysis figure that sample is made is as shown in Figure 3；Coating integral thickness is about 15-70 μm.Outside coating
Average Al content 28wt% at 1/3, average Si contents are 4.0wt%, and the addition of Si significantly improves the knot between coating and matrix
With joint efforts.
β-NiAl the coatings of Si modification obtained are subjected to thermal shock test, through 1000 times after 30 thermal shock tests, institute
There is coating sample not occur face checking and obscission.Fig. 6 shows that coating is cut after 30 thermal shock tests at 1000 DEG C
Face SEM patterns.
Embodiment 2
Workpiece is pre-processed, the pretreated step includes：Workpiece is subjected to dry blasting processing on sand-blasting machine,
Shot-peening uses the mixture of 120# emergies and glass sand, pressure 0.6MPa；It is clear by deionized water ultrasound to sandblasting sample
It washes spare.
Pretreated workpiece is placed in falcon tooth tooling, ensures that work piece inner surface way vent is smooth, by table in workpiece
Face channel is connected in the tooling equipped with aluminising source and fixes, under protection of argon gas (ventilatory capacity is (4L/min)/workpiece), adds
Heat keeps the temperature 2h to 1080 DEG C, 10 DEG C/min of heating rate, and the nickel in workpiece diffuses to work piece inner surface from inside to outside, in tooling
Aluminising source chemical vapor deposition to work piece inner surface, form the β-NiAl coatings that active element is modified；With β-NiAl coatings
Total weight, the β-NiAl coatings include Al elements 30wt%, Co element 6wt%, and surplus Ni, the Co are solid-solution in β-NiAl
In coating.
Wherein, the workpiece is directional solidification nickel-base high-temperature alloy DD5 materials, and ingredient is following (mass percent)：Co：
7.5, Cr：7, W：5, Mo：1.5, Al：6.2, Ta：6.5, Re：3, Ni：Surplus.
The aluminising source is existed by the ferroaluminium powder of the aluminum fluoride of 100g, the ammonium chloride of 50g, the cobalt powder of 500g, 19.35kg
It is obtained by the reaction at 1080 DEG C.
Principle is：
Co+2NH4Cl==CoCl2+2NH3(gas)+H2(gas)
The inner surface section metallograph that sample is made is as shown in Figure 2；As it can be seen that AlCo coating cross sections metallographs, aluminium in figure
Silicon coating surfacing, thickness overall distribution are uniform.
The inner surface section XPS analysis figure that sample is made is as shown in Figure 4；Coating integral thickness is about 15-70 μm.Outside coating
Average Al content 28wt% at 1/3, the addition of mean Co content 6.0wt%, Co significantly improve the antioxygenic property of coating,
The service life of coating can effectively be extended.
Embodiment 3
Workpiece is pre-processed, the pretreated step includes：Workpiece is subjected to dry blasting processing on sand-blasting machine,
Shot-peening uses the mixture of 120# emergies and glass sand, pressure 0.6MPa；It is clear by deionized water ultrasound to sandblasting sample
It washes spare.
Pretreated workpiece is placed in falcon tooth tooling, ensures that work piece inner surface way vent is smooth, by table in workpiece
Face channel is connected in the tooling equipped with aluminising source and fixes, under protection of argon gas (ventilatory capacity is (4L/min)/workpiece), adds
Heat keeps the temperature 5h to 1000 DEG C, 10 DEG C/min of heating rate, and the nickel in workpiece diffuses to work piece inner surface from inside to outside, in tooling
Aluminising source chemical vapor deposition to work piece inner surface, form the β-NiAl coatings that active element is modified；With β-NiAl coatings
Total weight, the β-NiAl coatings include Al elements 30wt%, Cr element 4wt%, and surplus Ni, the Cr are solid-solution in β-NiAl
In coating.
Wherein, the workpiece is DD5 materials, and ingredient is following (mass percent)：Co：7.5, Cr：7, W：5, Mo：1.5
Al：6.2, Ta：6.5, Re：3, Ni：Surplus.
The aluminising source is existed by the ferroaluminium powder of the aluminum fluoride of 100g, the ammonium chloride of 50g, the Cr powder of 500g, 19.35kg
1000 DEG C are obtained by the reaction.
Principle is：
Cr+2NH4Cl==CrCl2+NH3(gas)+H2(gas)
The coating integral thickness that sample is made is about 30 μm.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
1. β-NiAl the coatings that a kind of active element is modified, which is characterized in that with the total weight of β-NiAl coatings, the β-NiAl
Coating includes Al element 15-40wt%, active element 1-10wt%, surplus Ni.
2. β-NiAl the coatings that active element according to claim 1 is modified, wherein the active element is selected from Si, Co
At least one of with Cr.
3. the preparation method of β-NiAl coatings as claimed in claim 1 or 2, which is characterized in that the preparation method includes：
Work piece inner surface channel is connected in the tooling equipped with aluminising source, heating, heat preservation, under the protection of inert gas, work
Nickel in part diffuses to work piece inner surface from inside to outside, the aluminising source chemical vapor deposition in tooling to work piece inner surface, is formed
β-NiAl the coatings that active element is modified, wherein the workpiece is nickel base superalloy material；
Contain the halide of active element and the halide of Al in the aluminising source；
The aluminising source by 0.1-3wt% the metal powder of active element, the aluminum fluoride of 0.1-1wt%, 0.05-0.5wt%
Ammonium chloride, the ferroaluminium powder of surplus is obtained by the reaction at 900-1100 DEG C, and each weight percent is with the total weight of reactant
On the basis of.
4. preparation method according to claim 3, wherein the inert gas is argon gas.
5. preparation method according to claim 3, wherein the thickness of obtained β-NiAl coatings is 15-70 μm.
6. preparation method according to claim 3, wherein the ventilatory capacity of inert gas is (1-20L/min)/workpiece.
7. preparation method according to claim 3, wherein the time of chemical vapor deposition is 1-6h, temperature 900-
1100℃。
8. preparation method according to claim 3, wherein the preparation method includes the pre-treatment step of workpiece, described
The pre-treatment step of workpiece is：Workpiece is cleaned after dry blasting is handled.
9. preparation method according to claim 8, wherein the shot-peening used when dry blasting processing is emergy and/or glass
The pressure of glass sand, dry blasting processing is 0.4-0.8MPa.
10. a kind of cated workpiece of tool, which is characterized in that the coating is β-NiAl coatings as claimed in claim 1 or 2
And/or coating made from the preparation method described in any one of claim 3-9.
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| CN201810615393 | 2018-06-14 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112626449A (en) * | 2020-11-30 | 2021-04-09 | 中国航发动力股份有限公司 | Preparation method of chromium modified aluminide coating on turbine blade |
| CN114672761A (en) * | 2022-03-11 | 2022-06-28 | 沈阳梅特科航空科技有限公司 | Hollow blade inner and outer surface codeposition modified aluminide coating and preparation process thereof |
| CN114672761B (en) * | 2022-03-11 | 2024-06-28 | 沈阳梅特科航空科技有限公司 | Hollow blade inner and outer surface codeposition modified aluminide coating and preparation process thereof |
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| US6153313A (en) * | 1998-10-06 | 2000-11-28 | General Electric Company | Nickel aluminide coating and coating systems formed therewith |
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| CN102615876A (en) * | 2012-03-23 | 2012-08-01 | 上海大学 | Beta-NiAl thermal barrier coating with modified Pt+Si and method for preparing beta-NiAl thermal barrier coating |
| CN105624658A (en) * | 2014-10-31 | 2016-06-01 | 中国科学院金属研究所 | Active element modified aluminide coating and preparation process thereof |
| CN105624522A (en) * | 2014-10-31 | 2016-06-01 | 中国科学院金属研究所 | Single-phase platinum modified aluminide coating and preparation process thereof |
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2018
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| US6153313A (en) * | 1998-10-06 | 2000-11-28 | General Electric Company | Nickel aluminide coating and coating systems formed therewith |
| US20040180232A1 (en) * | 2003-03-12 | 2004-09-16 | General Electric Company | Selective region vapor phase aluminided superalloy articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112626449A (en) * | 2020-11-30 | 2021-04-09 | 中国航发动力股份有限公司 | Preparation method of chromium modified aluminide coating on turbine blade |
| CN114672761A (en) * | 2022-03-11 | 2022-06-28 | 沈阳梅特科航空科技有限公司 | Hollow blade inner and outer surface codeposition modified aluminide coating and preparation process thereof |
| CN114672761B (en) * | 2022-03-11 | 2024-06-28 | 沈阳梅特科航空科技有限公司 | Hollow blade inner and outer surface codeposition modified aluminide coating and preparation process thereof |
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| CN108660412B (en) | 2019-07-16 |
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