CN100519842C - Methd of preparing coating layer of gamma'Ni3Al /gamma-Ni - Google Patents
Methd of preparing coating layer of gamma'Ni3Al /gamma-Ni Download PDFInfo
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- CN100519842C CN100519842C CNB200610047020XA CN200610047020A CN100519842C CN 100519842 C CN100519842 C CN 100519842C CN B200610047020X A CNB200610047020X A CN B200610047020XA CN 200610047020 A CN200610047020 A CN 200610047020A CN 100519842 C CN100519842 C CN 100519842C
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- 239000011247 coating layer Substances 0.000 title abstract 8
- 229910001005 Ni3Al Inorganic materials 0.000 title abstract 5
- 229910003310 Ni-Al Inorganic materials 0.000 claims abstract description 37
- 238000009792 diffusion process Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910000851 Alloy steel Inorganic materials 0.000 claims abstract description 6
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 6
- 239000010962 carbon steel Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 93
- 239000011248 coating agent Substances 0.000 claims description 92
- 239000002114 nanocomposite Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 17
- 238000007747 plating Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 41
- 238000007254 oxidation reaction Methods 0.000 abstract description 41
- 239000002131 composite material Substances 0.000 abstract description 35
- 239000011253 protective coating Substances 0.000 abstract description 8
- 238000004070 electrodeposition Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 199
- 238000005266 casting Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 229910000943 NiAl Inorganic materials 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- 229910015372 FeAl Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 241000080590 Niso Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
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Abstract
This invention relates to a gamma'-Ni3Al/gamma-Ni coating layer, its preparation and application. The coating layer is composed of intermetallic compound phase gamma'-Ni3Al, and gamma-Ni matrix. The coating layer comprises Al 9.5-13 wt.%, and Ni as balance. The preparation method comprises: utilizing metal Ni, Fe or Co, carbon steel or low-alloy steel as the matrix, preparing nanoscale Ni-Al composite coating layer by composite electrodeposition, and performing vacuum diffusion heat treatment to obtain the gamma'-Ni3Al/gamma-Ni coating layer. The method is simple and mature, and is convenient for generalization. The coating layer has high adhesiveness to the matrix, and has high antioxidation performance. The gamma'-Ni3Al/gamma-Ni coating layer can be used as a protective coating layer for resisting high-temperature oxidation, and on controlled thermal growth of protective Al2O3 film at 600-1000 deg.C environmental temperature.
Description
Technical field
The present invention relates to coat preparing technology, specifically a kind of γ '-Ni
3Al/ γ-Ni coating and preparation and application.
Background technology
Intermetallic compound γ '-Ni with long range ordered structure
3Al has the better plasticity of metal and the good hot strength of pottery concurrently, also has resistance of oxidation preferably simultaneously.Receive much concern in the high temperature field for a long time.Its high temperature oxidation resistance mainly at high temperature can form based on higher Al content has low growth velocity, the Al of stable state
2O
3Oxide film.As high-temperature material of new generation, be widely used in the high temperature coating material in recent years.Obtain intermetallic compound Ni at present
3The Al coating mainly realizes by methods such as physical vapor deposition (for example magnetron sputtering), laser cladding, thermosprays.But the problem that exists is the preparation cost height of coating.In order to reduce the preparation cost of coating, the Ni-Al composite deposite that at first adopts composite electrodeposition technique preparation micron Al particle dispersion to distribute carries out the vacuum DIFFUSION TREATMENT then, can make γ '-Ni like this
3The Al disperse is distributed in the protective coating in γ-Ni matrix.But, because: the defect concentration height of (1) coating; (2) the γ '-Ni of disperse distribution
3Al can not form stable state successive Al in oxidising process
2O
3Oxide film.Therefore, be not widely used.
Summary of the invention
At above-mentioned deficiency, the purpose of this invention is to provide a kind of γ '-Ni
3Al/ γ-Ni coating and preparation and application.It passes through composite electrodeposition in advance, and the two-stage process of vacuum diffusion heat treatments obtains a kind of γ γ '-Ni then
3Al/ γ-Ni coating, thus its antioxidant property improved.
Technical scheme of the present invention is as follows:
γ '-Ni
3Al/ γ-Ni coating, its composition is by intermetallic compound phase γ '-Ni
3Al and γ-Ni matrix is formed, intermetallic compound phase γ '-Ni
3The Al disperse is distributed among matrix γ-Ni.By mass percentage, the content of Al is 9.5～13% in the coating, and all the other are Ni.
Being prepared as of coating " two step process methods " promptly is divided into latter two flow process earlier: be base material with the metal 1), on base material in advance with the method for coelectrodeposition by adding nanometer Al powder, preparation Ni-Al nano-composite plate; 2) with the method for vacuum diffusion heat treatments, make γ '-Ni
3Al/ γ-Ni alloying coating.Specific as follows:
With metal Ni or alloy material is base material, at first, adopts routine techniques, realizes the coelectrodeposition of Ni and nanometer Al powder, prepares nano-composite plate, i.e. the Ni-Al nano-composite plate.The plating bath of composite plating is a sulfate system, stirs up and down with 50～120rpm by porous plate in the coelectrodeposition process to make nanometer Al particle suspension in plating bath, and uniform deposition is at specimen surface; Bath temperature is 25～35 ℃, and current density is 1～4A/dm
2, electroplating time is 1.5～2 hours, the Al content in the coating is 10～20% mass percents.Secondly, the vacuum diffusion heat treatments is encapsulated into sample in the quartz glass tube that is full of argon gas, makes it be vacuum state.600 ℃～800 ℃ of temperature, time 3-10 hour.
Metal base of the present invention comprises Fe, Ni, Co, and carbon steel, low alloy steel, stainless steel, and other alloys.
γ ' of the present invention-Ni
3Al/ γ-Ni coating can be used as the protective coating of resistance to high temperature oxidation, is used for control heat growth successive protectiveness Al under 600 ℃～1000 ℃ envrionment temperatures
2O
3Oxide film; Can also being used for substituting diffusion, to ooze the Al coating be aluminide coating, or be used for other technology preparation at said temperature scope internal heat growth Al
2O
3The protective coating of membranous type can also be used for carbon steel, low alloy steel, austenite or ferritic stainless steel, Ti alloy, TiAl, FeAl base intermetallic compound.
Ultimate principle of the present invention is as follows:
The Ni based high-temperature alloy is widely used in the Aeronautics and Astronautics field.Intermetallic compound phase Ni
3Al has good high temperature oxidation resistance, so can by certain technology of preparing, its disperse be distributed in be used as the resistance to high temperature oxidation coating in the superalloy base material with it as particle.Form Ni
3The ultimate principle of Al is as follows: the present invention at first makes the Ni-Al nano-composite plate by the method for coelectrodeposition.Because prepared coating has unique nanostructure: promptly nanometer Al powder is dispersed in the nanometer Ni crystal grain, so under lower temperature (600 ℃～800 ℃), by the vacuum diffusion heat treatments, just can promote the mutual diffusion of Ni and Al and form tiny intermetallic compound Ni mutually
3Al, and even dispersion is distributed in γ-Ni matrix acquisition γ '-Ni
3Al/ γ-Ni coating.
Advantage of the present invention is as follows:
1, technology is simple, ripe, cost is low: the present invention prepares γ '-Ni by a kind of new " two step process "
3Al/ γ-Ni coating.Step 1-prepares the Ni-Al nano-composite plate: utilize composite plating technology that certain amount of nano Al particle is introduced in the Ni base coating, prepared Ni base composite cladding is a nanostructure.Because electronickelling is sophisticated technology, utilizes existing plating equipment, in tank liquor, add the nanometer Al powder of aequum, just can be made into this novel nano composite deposite, do not need other too much investment; Step 2-vacuum diffusion heat treatments: (600 ℃～800 ℃) at a certain temperature, by the vacuum DIFFUSION TREATMENT, make Ni, the mutual diffusion of Al phase in the nano-composite plate, chemical reaction takes place, generate intermetallic compound γ '-Ni with long range ordered structure
3Al, thus γ '-Ni obtained
3Al/ γ-Ni alloying coating.The present invention adopts vacuum DIFFUSION TREATMENT method, and cost is lower, and is very low to the requirement of workpiece shape, therefore, is of wide application.
2, γ ' of the present invention-Ni
3Al/ γ-Ni coating can be used as the protective coating of resistance to high temperature oxidation, is used for control heat growth successive protectiveness Al under 600 ℃～1000 ℃ envrionment temperatures
2O
3Oxide film; And alternative diffusion ooze the Al coating be aluminide coating or be used for the preparation of other technology at said temperature scope internal heat growth Al
2O
3The protective coating of membranous type can also be used for carbon steel, low alloy steel, austenite or ferritic stainless steel, Ti alloy, TiAl, FeAl base intermetallic compound.
Description of drawings
Fig. 1-1 is the surface topography of Ni-17Al (mass percent, the as follows) nano-composite plate of one embodiment of the invention.
Fig. 1-2 is the transmission electron microscope pattern of one embodiment of the invention Ni-Al nano-composite plate.
Fig. 1-3 is the surface topography of the Ni-17Al micron composite deposite of a comparative example of the present invention.
Fig. 1-4 is the cross section pattern of Ni-17Al (mass percent, the as follows) nano-composite plate of one embodiment of the invention.
Fig. 1-5 is the cross section pattern of Ni-17Al (mass percent, as follows) the micron composite deposite of one embodiment of the invention.
Fig. 2-1 is one embodiment of the invention γ '-Ni
3Al/ γ-Ni coating and two comparative examples, the γ '-Ni that adopts Ni-17Al micron composite deposite to prepare
3Al/ γ-Ni coating and casting Ni
3The XRD analysis comparison diagram of Al.
Fig. 2-2 is one embodiment of the invention γ '-Ni
3The cross section pattern of Al/ γ-Ni coating.
Fig. 2-3 adopts the γ '-Ni of Ni-17Al micron composite deposite preparation for comparative example of the present invention
3The cross section pattern of Al/ γ-Ni coating.
Fig. 3-1 is the oxidation weight gain comparison diagram one embodiment of the invention and other two comparative examples expose 20h in 1000 ℃ of air after.
Fig. 3-2 be one embodiment of the invention and other two comparative examples in 1000 ℃ of air, exposes oxidation weight gain behind the 20h square and the timing relationship comparison diagram.
Fig. 4 is one embodiment of the invention and other two comparative examples expose the zone of oxidation behind the 20h in 1000 ℃ of air an XRD analysis comparison diagram as a result.
Fig. 5-1 is a comparative example casting of the present invention Ni
3Expose zone of oxidation surface low power and high power (inserting figure) shape appearance figure behind the 20h in Al1000 ℃ of air.
Fig. 5-2 is one embodiment of the invention γ '-Ni
3Al/ γ-Ni coating exposes zone of oxidation surface low power and high power (the inserting figure) shape appearance figure behind the 20h in 1000 ℃ of air.
Fig. 5-3 adopts the γ '-Ni of Ni-17Al micron composite deposite preparation for comparative example of the present invention
3Zone of oxidation surface topography map in Al/ γ-1000 ℃ of air of Ni coating behind the exposure 20h.
Fig. 6-1 is comparative example Ni of the present invention
3Expose the zone of oxidation sectional view (low power and high power (inserting figure)) behind the 20h in Al1000 ℃ of air.
Fig. 6-2 is one embodiment of the invention γ '-Ni
3Al/ γ-Ni coating exposes the zone of oxidation sectional view (low power and high power (inserting figure)) behind the 20h in 1000 ℃ of air.
Fig. 6-3 adopts the γ '-Ni of Ni-17Al micron composite deposite preparation for comparative example of the present invention
3Zone of oxidation sectional view in Al/ γ-1000 ℃ of air of Ni coating behind the exposure 20h (low power and high power (inserting figure)).
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment
Present embodiment is with first electroplated Ni-Al nano-composite plate on Ni, and the vacuum diffusion heat treatments prepares γ '-Ni then
3Al/ γ-Ni coating is an example:
Its preparation method is: adopt conventional composite plating technology to prepare the Ni-Al composite deposite.Body material is metal_based materials such as Fe, Ni, Co, steel (carbon steel, low alloy steel, stainless steel), and other alloys.Plating bath is a sulfate system.Present embodiment is selected the low temperature modification plating bath for use, and preparation Ni-Al nano-composite plate carries out the vacuum diffusion heat treatments to it subsequently, prepares γ '-Ni
3Al/ γ-Ni coating.Its flow process is as follows:
Substrate metal → surface finish to 800
#Waterproof abrasive paper → surperficial ultrasonic cleaning → in the nickel plating bath that contains nanometer Al powder, carry out composite plating → acquisition Ni-Al composite deposite → vacuum diffusion heat treatments → obtain novel γ '-Ni
3Al/ γ-Ni coating.
When being plating, key of the present invention keep the Al particle suspension in tank liquor, control process parameters during DIFFUSION TREATMENT.Present embodiment adopts traditional composite plating facility and diffusion facilities to prepare.Specific as follows:
1) getting pure Ni is base material, is processed into the sample of 15 * 10 * 2mm size, is milled to 800 through silicon carbide paper
#Sand paper, ultrasonic cleaning in acetone;
2) the Al powder of selecting for use is a nano-scale, 60～100 nanometers.Particle is immersed in the bath soln earlier, so that particles dispersed is avoided reuniting;
3) electroplate liquid adopts the low temperature modification plating bath, and composition is as follows: 150g/l NiSO
47H
2O, 15g/l NH
4Cl, 15g/l H
3BO
3, the 0.1g/l sodium lauryl sulphate; The solution of configuration was placed 24 hours through fully stirring after-filtration; The pH value of solution value can be used in 5.4～5.6 scopes;
4) electrodeposition process adopts plate pump formula device to stir plating bath, is suspended in the plating bath to guarantee plating bath middle-weight rare earths oxide particle, and uniform deposition is at specimen surface; Bath temperature is 30 ℃, and current density is 2A/dm
2, stirring velocity is 75rpm.Electroplating time is 2 hours, and the sample mean thickness of coating is 60 μ m, and the Al compounding quantity is 10～20% mass percents;
5) vacuum diffusion heat treatments then.The Ni-Al nano-composite plate is put in the quartz glass tube of argon gas for protection gas, and putting into retort furnace then heats, 600 ℃～800 ℃ of temperature, time 3-10 hour.By DIFFUSION TREATMENT, make Ni, the mutual diffusion of Al phase in the nano-composite plate, thereby form novel γ '-Ni
3Al/ γ-Ni coating.Coated component is by intermetallic compound phase γ '-Ni
3Al and γ-Ni matrix is formed; By mass percentage, Al content is 9.5～13% in the coating, and all the other are Ni.
Be the result of type i of the present invention and two embodiment of Type II below:
1) Ni-Al nano-composite plate structure
Fig. 1-the 1st, the surface topography of Ni-Al nano-composite plate can see that particle is evenly distributed in the Ni base.Fig. 1-2 is the TEM pattern of Ni-Al nano-composite plate, and as can be seen, circular nanometer Al particle is distributed in the nanometer crystalline Ni matrix evenly distributedly, the maximum about 120nm of particle, and minimum about 60nm, the median size size is approximately 85nm.Compare (Fig. 1-3) with the pattern of congruent Ni-Al micron composite deposite, the surface ratio of Ni-Al nano-composite plate is more smooth.Compare the cross section pattern of Ni-Al nano-composite plate (Fig. 1-4) and micron composite deposite (Fig. 1-5), even, tiny nanometer Al particle dispersion is distributed in the Ni matrix.
2) γ '-Ni
3The weave construction of Al/ γ-Ni coating
Fig. 2-1 is novel γ '-Ni
3Al/ γ-Ni coating and the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating and casting Ni
3The X-ray analysis result of Al.As seen, after 4 hours, Al no longer is present in the coating with the form of second phase Ni-Al nano-composite plate, but is present in γ-Ni and γ '-Ni through 600 ℃ of diffusions
3Among the Al, coating has the (Ni by γ '
3Al) and the alloy structure formed of γ (Ni).Fig. 2-2 is γ '-Ni
3The cross section pattern of Al/ γ-Ni coating, as seen through 600 ℃, after the mutual diffusion of 4 hours nanometer Al particles and the Ni reaction, tiny γ '-Ni
3Al phase (grey form and aspect) forms, and is evenly dispersed among γ-Ni.The γ ' of gained-Ni after the vacuum diffusion heat treatments
3In Al/ γ-Ni coating, the Al mass content is 9.5～13% (present embodiment is 9.5%).In the DIFFUSION TREATMENT process,, make the γ '-Ni after the alloying because mutual diffusion can take place for coating and matrix Ni
3Al mass content the lacking of Al/ γ-Ni coating than former Ni-Al coating.And the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating (Fig. 2-3), thick γ '-Ni
3Al is distributed among γ-Ni mutually unevenly.Experiment showed, that the present invention adopts nanometer Al particle, and when adopting aforesaid method to make Al mass content in the coating be 9.5～13% scopes, all can obtain γ '-Ni
3Al/ γ-Ni coating.
Oxidation susceptibility under 1000 ℃
Present embodiment provides the novel γ ' of the present invention-Ni
3Al/ γ-Ni coating and the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating and casting Ni
3Al is performance behind the oxidation 20h and pattern (preparation method is the same) in 1000 ℃ of air.
The high temperature oxidation experiment is that the model that adopts Thermo Cahn company to produce is the TGA instrument of TherMax700, and temperature rise rate is 50 ℃/min, and 1000 ℃ are incubated 20 hours, then furnace cooling.Fig. 3-1 is novel γ '-Ni
3Al/ γ-Ni coating, the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating and casting Ni
3The Al20h oxidation weight gain relatively.On scheming, can see the γ '-Ni that adopts the preparation of Ni-Al micron composite deposite
3The rate of oxidation of Al/ γ-Ni coating is the fastest, and γ ' of the present invention-Ni
3The rate of oxidation of Al/ γ-Ni coating obviously descends, with casting Ni
3The rate of oxidation of Al is suitable.Fig. 3-2 be the weightening finish of 20 hours unit surfaces of above three kinds of sample oxidations square with the time relation comparison diagram.As seen, except the oxidation initial stage, γ ' of the present invention-Ni
3Al/ γ-Ni coating, the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating and casting Ni
3The rate of oxidation of Al is all followed the parabola-growth rule.Table 1 is that 20 hours the parabolic rate constant of being calculated of three kinds of sample oxidations relatively after exposing 20h in 1000 ℃ of air.Wherein, γ ' of the present invention-Ni
3Al/ γ-Ni coating is with casting Ni
3The para-curve constant of Al is more approaching.And the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating oxidation weightening finish is very fast.As seen, γ ' of the present invention-Ni
3Al/ γ-Ni coating is than the γ '-Ni that adopts the preparation of Ni-Al micron composite deposite
3Al/ γ-Ni coating has better antioxidant property.
Table 1
Fig. 4 is γ ' of the present invention-Ni
3Al/ γ-Ni coating, the γ '-Ni that adopts Ni-Al micron composite deposite to prepare
3Al/ γ-Ni coating and casting Ni
3Al is in the XRD facies analysis result of 20 hours rear oxidation films of 1000 ℃ of constant temperature oxidations, as seen, and at γ ' of the present invention-Ni
3Al/ γ-formed oxide compound of Ni coating with the casting Ni
3The oxide compound of the last formation of Al is close, by α-Al
2O
3, NiAl
2O
4And NiO forms.And at the γ '-Ni that adopts the preparation of Ni-Al micron composite deposite
3The oxide compound that forms on Al/ γ-Ni coating mainly is made up of NiO.Be respectively casting Ni as Fig. 5-1 and Fig. 5-2
3Al and γ ' of the present invention-Ni
3Al/ γ-the surface topography of Ni coating oxidation after 20 hours, energy spectrum analysis shows that the oxide compound that is generated is the oxide compound of rich aluminium.By contrast at the γ '-Ni that adopts the preparation of Ni-Al micron composite deposite
3Form the oxide compound of rich Ni on Al/ γ-Ni coating, this point can exist the oxide compound of a large amount of nickel to be confirmed from the oxide film surface (shown in Fig. 5-3).
Fig. 6-1 is casting Ni
3Al is in 1000 ℃ of constant temperature oxidations corresponding cross section pattern after 20 hours.The section structure morphology analysis result of oxide film shows that formed oxide film has layered structure: outer is gray NiAl
2O
4, internal layer is the α-Al of black
2O
3
Fig. 6-2 is γ ' of the present invention-Ni
3Al/ γ-Ni coating is in the cross section pattern of 1000 ℃ of constant temperature oxidations after 20 hours.As seen, oxide film has with casting Ni
3The layered structure that Al is similar, promptly skin is gray NiAl
2O
4(minor N iO is arranged), internal layer are the α-Al of black
2O
3The XRD facies analysis result of this experimental result and front matches.
Fig. 6-3 is for adopting the γ '-Ni of Ni-Al micron composite deposite preparation
3Al/ γ-Ni coating is in 1000 ℃ of constant temperature oxidations corresponding cross section pattern after 20 hours.Section structure shows that its oxide film structure is: loose, porous NiO skin, discontinuous black α-Al
2O
3And the inner oxide internal layer of Al.
Above analytical results shows: γ ' of the present invention-Ni
3Al/ γ-Ni coating has than the γ '-Ni that adopts the preparation of Ni-Al micron composite deposite
3Al/ γ-better the antioxidant property of Ni coating has and casting Ni
3The antioxidant property that the Al alloy phase contends with.Why produce such result, closely related with the structure of these two kinds of coatings.
For casting Ni
3The Al alloy, at the oxidation initial stage, NiO and Al
2O
3Meeting is forming core simultaneously, because Ni
3The Al alloy contains enough Al, in a short period of time protectiveness Al
2O
3Oxide film just can form.Thereby suppressed the continued growth of NiO.And the NiO and the Al that form in the early stage
2O
3Form NiAl by solid state reaction
2O
4Thereby, form double-deck oxide film: the outer NiAl of being
2O
4, internal layer is Al
2O
3γ ' of the present invention-the Ni that why has the different tissues structure
3Al/ γ-Ni coating and casting Ni
3Does the Al alloy but have similar oxidation susceptibility? for γ ' of the present invention-Ni
3Although Al/ γ-Ni coating is Ni
3The volume fraction of Al is well below casting Ni
3The Al alloy, still, it has particular structure: even, tiny γ '-Ni
3The Al disperse is distributed in the Ni matrix.At the oxidation initial stage, NiO and Al
2O
3With the Ni matrix on coatingsurface and γ '-Ni respectively
3The last formation of Al is because γ '-Ni
3Al very tiny mutually (due to nanometer Al particle and the Ni reaction) is distributed in the γ '-Ni in the Ni matrix
3The distance of Al phase is also very little, the Al of formation
2O
3Internuclear distance also shortens, like this, and Al
2O
3Examine quick transverse growth and form successive protectiveness Al
2O
3The time of oxide film also shortens thereupon.In case the Al of protectiveness
2O
3Oxide film forms, and the continued growth of NiO is suppressed, its oxidising process and casting Ni
3The oxidation of Al alloy is similar.Equally, can explain the γ '-Ni for preparing by Ni-Al micron composite deposite
3Why Al/ γ-Ni coating can not form successive Al in oxidising process
2O
3Oxide film.At the oxidation initial stage, NiO and Al
2O
3With the Ni matrix on coatingsurface and γ '-Ni respectively
3The last formation of Al is because γ '-Ni
3Al very thick mutually (due to micron A1 particle and the Ni reaction) is at identical γ '-Ni
3Under the prerequisite of Al phase volume fraction, be distributed in the γ '-Ni in the Ni matrix
3The distance of Al phase very big (this point can be from Fig. 2-2, and 2-3 can clearly find out), the Al of formation
2O
3Internuclear distance also increases thereupon, Al
2O
3Examine quick transverse growth and form continuous protectiveness Al
2O
3Required time of oxide film is also elongated, at the oxidation initial stage, can not form continuous protectiveness Al fast
2O
3Oxide film, NiO ramp, inwardly diffusion rapidly of oxygen simultaneously, the inner oxide of formation Al.Exactly the result with Fig. 6-3 is consistent for this.
γ ' of the present invention-Ni
3Al/ γ-Ni coating can be used as the protective coating of resistance to high temperature oxidation (or corrosion), for example, is used for 600 ℃～1000 ℃ steel that antioxidant property is relatively poor, and anti-oxidant (or corrosion) coating of metal Ni, Co, Fe etc.And this coating is expected to be used for the heat growth Al of some component of aircraft engine
2O
3The protective coating of membranous type.
Claims (5)
1, a kind of γ '-Ni
3The preparation method of Al/ γ-Ni coating is characterized in that: this coating is the alloying coating, and its coated component is by intermetallic compound phase γ '-Ni
3Al and γ-Ni matrix is formed; By mass percentage, Al content is 9.5～13% in the coating, and all the other are Ni;
Being prepared as of coating " two step process methods " promptly is divided into latter two flow process earlier: be base material with the metal 1), on base material in advance with the method for coelectrodeposition by adding nanometer Al powder, preparation Ni-Al nano-composite plate; 2) with the method for vacuum diffusion heat treatments, make γ '-Ni
3Al/ γ-Ni alloying coating;
Described metal base comprises Fe, Ni, Co, carbon steel, low-alloy steel or stainless steel.
2, according to the described γ ' of claim 1-Ni
3The preparation method of Al/ γ-Ni coating is characterized in that: wherein flow process 1) the Ni-Al nano-composite plate in, by mass percentage, Al is 10～20%, all the other are Ni.
3, according to the described γ ' of claim 1-Ni
3The preparation method of Al/ γ-Ni coating is characterized in that: make nanometer Al particle suspension in plating bath by stirring in the coelectrodeposition process, uniform deposition is at specimen surface; Bath temperature is 25～35 ℃, and current density is 1～4A/dm
2, electroplating time is 1.5～4 hours.
4, according to the described γ ' of claim 1-Ni
3The preparation method of Al/ γ-Ni coating is characterized in that: wherein flow process 2) γ '-Ni of adopting the vacuum diffusion heat treatments to make
3The alloying coating of γ-Ni that the Al disperse distributes, by mass percentage, wherein Al content 9.5～13%.
5, according to claim 1 or 4 described γ '-Ni
3The preparation method of Al/ γ-Ni coating; it is characterized in that: described vacuum diffusion heat treatments is the Ni-Al nano-composite plate to be put into be full of in the quartz glass tube of argon gas for protection gas; put into retort furnace then and heat, 600 ℃～800 ℃ of temperature, time 3-10 hour.
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| CN101994077A (en) * | 2010-10-27 | 2011-03-30 | 江苏科技大学 | High-temperature oxidation resisting intermetallic compound coating and preparation method thereof |
| CN102115864A (en) * | 2010-12-21 | 2011-07-06 | 苏州雅典娜科技有限公司 | High-temperature-resistant protective coating |
| CN102776546B (en) * | 2011-05-11 | 2015-03-18 | 中国科学院金属研究所 | High temperature oxidation resistant NiAl-Y2O3 coating, its preparation method and its application |
| WO2017039460A1 (en) * | 2015-09-02 | 2017-03-09 | Auckland Uniservices Limited | A plating or coating method |
| CN113075053B (en) * | 2021-03-31 | 2023-02-17 | 华能国际电力股份有限公司 | Method and system for rapidly predicting long-term thermal exposure tensile strength of Ni3Al reinforced alloy |
| CN114250432B (en) * | 2021-12-22 | 2023-10-27 | 北京钢研高纳科技股份有限公司 | Cracking prevention method for superalloy disc or ring and application thereof |
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