CN106637071A - Method for preparing composite coating by adopting multi-stage pack cementation aluminizing in combination with micro-arc oxidation - Google Patents
Method for preparing composite coating by adopting multi-stage pack cementation aluminizing in combination with micro-arc oxidation Download PDFInfo
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- CN106637071A CN106637071A CN201611019243.5A CN201611019243A CN106637071A CN 106637071 A CN106637071 A CN 106637071A CN 201611019243 A CN201611019243 A CN 201611019243A CN 106637071 A CN106637071 A CN 106637071A
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- arc oxidation
- composite coating
- base material
- pack cementation
- coating
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- 239000011248 coating agent Substances 0.000 title claims abstract description 73
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000005269 aluminizing Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 title abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 33
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 31
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000009413 insulation Methods 0.000 claims description 16
- 239000010955 niobium Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 239000011253 protective coating Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- -1 Rare earth salt Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/48—Aluminising
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Physical Vapour Deposition (AREA)
- Nonmetallic Welding Materials (AREA)
Abstract
The invention discloses a method for preparing a composite coating by adopting multi-stage pack cementation aluminizing in combination with micro-arc oxidation and belongs to the technical field of high-temperature protective coatings. A continuous and smooth NbAl3 aluminized layer is obtained firstly on a substrate with a multi-stage pack cementation aluminizing technology; a micro-arc oxidation electrolyte is regulated by adding film-forming agent sodium fluoride, modifier sodium tungstate, stabilizer EDTA-2Na and rare-earth salt yttrium nitrate; and a uniform and regular porous Al2O3 ceramic film layer is prepared on the NbAl3 aluminized layer, and the Al2O3/NbAl3 composite coating is obtained. The Al2O3/NbAl3 composite coating has the characteristics of good bonding performance, uniform coating and excellent high-temperature hot corrosion resistance, the coating with different thicknesses can be obtained by controlling pack cementation aluminizing time and temperature as well as the electrolyte and electrical parameters of the micro-arc oxidation, the process is simple, and the controllability is high.
Description
Technical field
The invention belongs to high-temperature protection coating technical field, is related to a kind of multisection type pack cementation aluminizing and prepares with reference to differential arc oxidation
The method of composite coating.
Background technology
High-temperature protection coating is mainly used in the gas turbine hot-end component of Aero-Space and modern energy industrial circle.Gold
Category niobium（Nb）Fusing point is high（2468℃）, medium density（8.6g/cm3）, high temperature specific strength it is big, with excellent mechanical behavior under high temperature
And processing characteristics, niobium alloy is one of important candidate material of high-temperature structural material.But the non-oxidizability of niobium alloy is poor, therefore
Coating of the niobium alloy surface coating with protectiveness is most important.Differential arc oxidation passes through electrochemistry, heat chemistry and plasma
Deng collective effect, can be in the floor height hardness of material surface in-situ preparation one, wear-resisting, anti-corrosion ceramic membrane.Wang Rongli and Norlin
Deng using differential arc oxidization technique in one layer of cavernous Nb of pure Nb Surface Creations2O5Film layer.But Nb2O5 It is big with the volume ratio of Nb
（About 2.74）, very big internal stress can be caused under high temperature, it is easily caused film layer cracking and comes off and lose protective action.And the work of aluminium
Property it is very high, the pellumina of densification is easily combined to form with oxygen at high temperature to stop the inside diffusion of oxygen.If can exist in advance
Niobium alloy prepares one layer of al-containing layers, recycles differential arc oxidization technique also to obtain Al2O3Film.Rare earth element has outside special core
Electronic structure, frequently as additive application in field of surface treatment.The research such as Hong Shangkun finds, adds in micro-arc oxidation electrolyte
Ce(NO3)3The compactness of film layer can be significantly improved, its thickness, hardness and wearability is improved.Rare earth salt additives are to differential arc oxidation
The performance of ceramic membrane has a great impact, and presently relevant research is concentrated mainly on Al, Mg alloy, to the micro- of pack cementation aluminizing niobium alloy
Arc oxidation technology and sign are unclear, and its High Temperature Hot-corrosion Behaviorof performance is rarely reported.
The content of the invention
It is an object of the invention to provide a kind of method that multisection type pack cementation aluminizing prepares composite coating with reference to differential arc oxidation, should
Composite coating can be applied to high-temperature thermal oxidation and heat erosion field as protective coating.
The technical scheme is that：A kind of method that multisection type pack cementation aluminizing prepares composite coating with reference to differential arc oxidation,
Comprise the following steps：
（1）Pretreatment：It is cleaned by ultrasonic 12～15min with acetone after base material is polished step by step, dries up；
（2）The process of multisection type pack cementation aluminizing：First aluminizing medium is prepared as following weight percent：For aluminium agent 9～11wt% of aluminium powder,
Activator is fluorinated 2～4wt% of sodium powder and filler 85～89wt% of alumina powder, is then mixed using ball mill, then will fully mix
Even aluminizing medium and base material is sealed in together in ceramic crucible, is finally placed in vacuum tube furnace, arrange parameter：Vacuum is
3.5×10-2The heating rate of～7.0Pa, 9～11 DEG C/min rise to 120～150 DEG C insulation 1h, 300 ~ 350 DEG C insulation 2h, 900
～1000 DEG C of 2～6h of insulation, then room temperature is cooled to the furnace to after 400 ~ 500 DEG C with the cooldown rate of 9～11 DEG C/min, obtain
NbAl3The aluminising base material of aluminized coating；
（3）Differential arc oxidation process：From dipulse high voltage power supply as pressure source, aluminising base material is hung on into anode, with stainless
Used as negative electrode, aluminising base material is immersed in electrolyte to steel tank, and compound additive electrolyte is by 10～14g/L of sodium metaaluminate, hydroxide
2～6g/L of sodium, 2～6g/L of sodium fluoride, the g/L of sodium tungstate 4～8,1～3g/L of disodium ethylene diamine tetraacetate, 1～4g/L of yttrium nitrate
Composition；Differential arc oxidation process is carried out using constant voltage mode, electrical quantity is set：360～400V of positive voltage, positive dutycycle 10～20%,
300～500Hz of frequency；And apply mechanical agitation, solution temperature control at 30～35 DEG C, process time be after 20～60min
Aluminising base material plates last layer Al2O3Ceramic membrane, is obtained Al2O3 / NbAl3Composite coating.
The base material is niobium or niobium alloy, the NbAl3The thickness of aluminized coating is 50～110 μm, Al2O3The thickness of ceramic membrane
Spend for 6～15 μm.
Beneficial effects of the present invention：
1. the composite coating that the present invention is prepared using multisection type pack cementation aluminizing and differential arc oxidization technique, surface forms loose structure
Ceramic membrane, micropore distribution is relatively regular, and coating and niobium alloy base material are well combined.
2. the pack aluminizing in the composite coating takes interim low-temperature insulation technology, and contributing to reduction base material should
Power and to surface pre-activate, can obtain the NbAl of continuous formation in niobium or niobium alloy base material3Aluminized coating.
3. micro-arc oxidation electrolyte passes through to add film forming agent sodium fluoride, modifying agent sodium tungstate, stabilizer in the composite coating
Disodium ethylene diamine tetraacetate and rare-earth salts yttrium nitrate, particularly rare-earth salts yttrium nitrate Y (NO3)3Oxide thickness and enhancing can be increased
The adhesiveness of oxide-film, so as to improve compactness, electrolyte stability and the film hardness of film layer.
4. the composite coating can effectively extend the service life of niobium or niobium alloy under High Temperature Hot-corrosion Behaviorof.Coating mainly by
NbAl3And Al2O3Composition, generates a large amount of cubic structure NaNbO not of uniform size under High Temperature Hot-corrosion Behaviorof3, differential arc oxidation it is micro-
Hole almost disappears, and hinders fused salt inwardly to spread, and shows good corrosion and heat resistant.
5. the painting of different-thickness can be obtained by control pack cementation aluminizing time, temperature and micro-arc oxidation electrolyte, electrical quantity
Layer, process is simple, controllability is strong.
Description of the drawings
Fig. 1 is the Al of the embodiment of the present invention 12O3 / NbAl3The XRD spectrum of composite coating.
Fig. 2 is the Al of the embodiment of the present invention 12O3 / NbAl3The surface topography of composite coating.
Fig. 3 is the Al of the embodiment of the present invention 12O3 / NbAl3The Cross Section Morphology of composite coating.
Fig. 4 is the Al of the embodiment of the present invention 12O3 / NbAl3XRD spectrum of the composite coating in 900 DEG C of heat erosion 50h.
Fig. 5 is the Al of the embodiment of the present invention 12O3 / NbAl3Surface topography of the composite coating in 900 DEG C of heat erosion 50h.
Fig. 6 is the Al of the embodiment of the present invention 22O3 / NbAl3The surface topography of composite coating.
Fig. 7 is the Al of the embodiment of the present invention 22O3 / NbAl3The Cross Section Morphology of composite coating.
Fig. 8 is the Al of Example 1 and Example 2 of the present invention2O3 / NbAl3Composite coating is with niobium alloy base material at 900 DEG C
The surrosion curve of heat erosion 50h.
Fig. 9 is Al of the present invention2O3 / NbAl3The each element content of composite coating surface by micro-arc oxidation film layer.
Figure 10 is that multisection type pack cementation aluminizing of the present invention prepares NbAl3The surface topography of aluminized coating
Figure 11 is that multisection type pack cementation aluminizing of the present invention prepares NbAl3The Cross Section Morphology of aluminized coating.
Sequence number in Fig. 3 and Fig. 7 is respectively：A. Al2O3Ceramic membrane；B. NbAl3Aluminized coating；C. niobium alloy base material.
Specific embodiment
With reference to specific embodiment and accompanying drawing, the invention will be further described, but does not limit the scope of the invention
And range of application.
First, multisection type pack cementation aluminizing in niobium alloy surface combines compound additive differential arc oxidation preparation method
Embodiment 1
A kind of niobium alloy surface multisection type pack cementation aluminizing combines compound additive differential arc oxidation preparation method, including following operation step
Suddenly：
1. pre-process：Base material selects niobium alloy C103, and its chemical composition is：Hf 10.0, Ti 1.30, Zr 0.34, W 0.34,
Ta 0.30, C 0.005, N 0.014, O 0.013, Nb surplus（wt.%）, it is cleaned by ultrasonic 12min with acetone after polishing step by step, blow
It is dry；
2. multisection type pack cementation aluminizing is processed：First aluminizing medium is prepared as following weight percent：For aluminium agent aluminium powder 10wt%, activation
Agent is fluorinated sodium powder 3wt% and filler alumina powder 87wt%, is then mixed using ball mill, then by the abundant aluminizing medium for mixing and
Base material is sealed in together in ceramic crucible, is finally placed in vacuum tube furnace, is evacuated to 3.5 × 10-2Pa, with 10 DEG C/min's
Heating rate rises to 120 DEG C of insulation 1h, 300 DEG C of insulation 2h, 940 DEG C of insulation 4h, then with the cooldown rate of 10 DEG C/min to 500 DEG C
After cool to room temperature with the furnace, obtain NbAl3The aluminising niobium alloy of aluminized coating；
3. differential arc oxidation is processed：From dipulse high voltage power supply as pressure source, aluminising niobium alloy is hung on into anode, with stainless
Used as negative electrode, aluminising niobium alloy is immersed in electrolyte to steel tank, and compound additive electrolyte is by sodium metaaluminate 12g/L, NaOH
4g/L, sodium fluoride 4g/L, the g/L of sodium tungstate 6, disodium ethylene diamine tetraacetate 2g/L, yttrium nitrate 3g/L compositions；Using constant voltage mode
Differential arc oxidation process is carried out, and applies mechanical agitation, 30 DEG C of solution temperature, process time 30min；And by following parameter regulation electricity
Parameter：Positive voltage 380V, positive dutycycle 10%, frequency 400Hz, differential arc oxidation process obtains Al2O3 / NbAl3Composite coating, it is multiple
It is 102 μm to close coating layer thickness.
Embodiment 2
1. pre-process：Base material selects niobium alloy C103, and its chemical composition is：Hf 10.0, Ti 1.30, Zr 0.34, W 0.34,
Ta 0.30, C 0.005, N 0.014, O 0.013, Nb surplus（wt.%）, it is cleaned by ultrasonic 15min with acetone after polishing step by step, blow
It is dry；
2. multisection type pack cementation aluminizing is processed：First aluminizing medium is prepared as following weight percent：For aluminium agent aluminium powder 11wt%, activation
Agent is fluorinated sodium powder 4wt% and filler alumina powder 85wt%, is then mixed using ball mill, then by the abundant aluminizing medium for mixing and
Base material is sealed in together in ceramic crucible, is finally placed in vacuum tube furnace, is evacuated to 1.3 × 10-1Pa, with 10 DEG C/min's
Heating rate rises to 150 DEG C of insulation 1h, 350 DEG C of insulation 2h, 940 DEG C of insulation 4h, then with the cooldown rate of 10 DEG C/min to 400 DEG C
After cool to room temperature with the furnace, obtain NbAl3The aluminising niobium alloy of aluminized coating；
3. differential arc oxidation is processed：From dipulse high voltage power supply as pressure source, aluminising niobium alloy is hung on into anode, with stainless
Used as negative electrode, aluminising niobium alloy is immersed in electrolyte to steel tank, and compound additive electrolyte is by sodium metaaluminate 12g/L, NaOH
4g/L, sodium fluoride 4g/L, sodium tungstate 4g/L, disodium ethylene diamine tetraacetate 2g/L, yttrium nitrate 3.5g/L compositions；Using constant voltage mode
Differential arc oxidation process is carried out, and applies mechanical agitation, 31 DEG C of solution temperature, process time 20min；And by following parameter regulation electricity
Parameter：Positive voltage 360V, positive dutycycle 15%, frequency 600Hz, then the sample after pack cementation aluminizing is hung in electrolyte, the differential of the arc
Oxidation processes obtain Al2O3 / NbAl3Composite coating, composite coating thickness is 70 μm.
Embodiment 3
1. pre-process：Base material selects niobium alloy C103, and its chemical composition is：Hf 10.0, Ti 1.30, Zr 0.34, W 0.34,
Ta 0.30, C 0.005, N 0.014, O 0.013, Nb surplus（wt.%）, it is cleaned by ultrasonic 15min with acetone after polishing step by step, blow
It is dry；
2. multisection type pack cementation aluminizing is processed：First aluminizing medium is prepared as following weight percent：For aluminium agent aluminium powder 9wt%, activator
Fluorination sodium powder 2wt% and filler alumina powder 89wt%, is then mixed using ball mill, then by the abundant aluminizing medium for mixing and base
Material is sealed in together in ceramic crucible, is finally placed in vacuum tube furnace, is evacuated to 4.0Pa, with the intensification speed of 10 DEG C/min
Rate rise to 120 DEG C insulation 1h, 300 DEG C insulation 2h, 940 DEG C insulation 3h, then with the cooldown rate of 10 DEG C/min to after 400 DEG C with stove
Room temperature is cooled to, NbAl is obtained3The aluminising niobium alloy of aluminized coating；
3. differential arc oxidation is processed：From dipulse high voltage power supply as pressure source, aluminising niobium alloy is hung on into anode, with stainless
Used as negative electrode, aluminising niobium alloy is immersed in electrolyte to steel tank, and compound additive electrolyte is by sodium metaaluminate 12g/L, NaOH
4g/L, sodium fluoride 4g/L, sodium tungstate 4g/L, disodium ethylene diamine tetraacetate 2g/L, yttrium nitrate 4g/L compositions；Entered using constant voltage mode
The process of row differential arc oxidation, and apply mechanical agitation, 32 DEG C of solution temperature, process time 60min；And join by following parameter regulation electricity
Number：Positive voltage 400V, positive dutycycle 20%, frequency 300Hz, then the sample after pack cementation aluminizing is hung in electrolyte, differential of the arc oxygen
Change is processed and obtains Al2O3 / NbAl3Composite coating, composite coating thickness is 100 μm.
2nd, multisection type pack cementation aluminizing in niobium alloy surface combines the structural characterization of compound additive differential arc oxidation preparation method
By embodiment 1 and Al obtained in embodiment 22O3 / NbAl3Composite coating, is utilized respectively the thing that XRD diffraction detects coating
Phase structure, using ESEM（SEM）The surface of observation coating and Cross Section Morphology, before observation coating cross sections, in advance with chemistry
It is plated in specimen surface and prepares a Ni-P layers, shields.Measurement result refers to Fig. 1～Figure 11.
1. the measurement result situation of embodiment 1.
As shown in Figure 1：Al2O3 / NbAl3Composite coating is mainly by NbAl3With γ-Al2O3Phase composition, illustrates aluminising process
NbAl formed and diffusion reaction with the Al powder of outer layer in middle niobium alloy base material there is3Phase, and differential arc oxidation is in NbAl3Generate on aluminized coating
Al2O3Ceramic membrane, and it is not detected by the thing phase containing Y.
As shown in Figure 2：Al2O3 / NbAl3Composite coating surface is in loose structure, adds additive yttrium nitrate Y (NO3)3Can
The differential arc oxidation micropore of more uniform rule is obtained, the quantity of micropore and aperture are more or less the same.
As shown in Figure 3：Al2O3Ceramic membrane and NbAl3Aluminized coating, NbAl3Aluminized coating and base material are well combined；NbAl3Aluminising
Layer even compact, Al2O3Ceramic membrane is in cellular.
As shown in Figure 4：The 75wt%Na that 900 DEG C of Jing2SO4After 25wt%NaCl mixed melting salt hot corrosion 50h, Al2O3 /
NbAl3Composite coating is mainly by NaNbO3、Al2O3With Nb phase compositions.
As shown in Figure 5：The 75wt%Na that 900 DEG C of Jing2SO4After 25wt%NaCl mixed melting salt hot corrosion 50h, Al2O3 /
NbAl3The a large amount of NaNbO not of uniform size of composite coating surface sediment3, the micropore of differential arc oxidation almost disappears, shows good
Corrosion and heat resistant.
As shown in Figure 8：The Al of embodiment 12O3 / NbAl3The 75wt%Na that 900 DEG C of composite coating Jing2SO4And 25wt%NaCl
Gain in weight after mixed melting salt hot corrosion 50h is 45.59mg/cm2；And the gain in weight after niobium alloy base material heat erosion 50h is
253.10mg/cm2, illustrate Al2O3 / NbAl3The hot corruption of high temperature resistance of composite coating is good, and through calculating 5～6 times are improved.
As shown in Figure 9：Al2O3 / NbAl3Composite coating surface by micro-arc oxidation film layer mainly contains Al, Nb, O element, and
Containing a small amount of Y element.And Na elements receive Y (NO3)3Impact it is little, change is little；Y and Nb elements, with Y (NO3)3Concentration
Increase and increase；O and Al elements are then with Y (NO3)3The increase of concentration and reduce.
As shown in Figure 10：The NbAl that multisection type pack cementation aluminizing is obtained3Aluminized coating surfacing.
As shown in Figure 11：The NbAl that multisection type pack cementation aluminizing is obtained3Aluminized coating continuous uniform, is well combined.
2. the measurement result situation of embodiment 2.
As shown in Figure 6：Al2O3 / NbAl3Composite coating surface by micro-arc oxidation micropore is uniformly regular, the quantity of micropore and hole
Footpath is more or less the same, surface attachment white particle.
As shown in Figure 7：Al2O3 / NbAl3NbAl in composite coating3Aluminized coating and Al2O3Ceramic membrane, niobium alloy base material
It is well combined, continuous uniform.
As shown in Figure 8：The Al of embodiment 22O3 / NbAl3The 75wt%Na that 900 DEG C of composite coating Jing2SO4And 25wt%NaCl
Gain in weight after mixed melting salt hot corrosion 50h is 50.01mg/cm2；And the gain in weight after niobium alloy base material heat erosion 50h is
253.10mg/cm2, illustrate Y-Al2O3 / NbAl3The hot corruption of high temperature resistance of composite coating is good, and through calculating 5～6 times are improved.
As shown in Figure 9：Al2O3 / NbAl3Composite coating surface by micro-arc oxidation film layer is mainly made up of Al, Nb, O element,
And containing a small amount of Y, Na element.
Claims (3)
1. a kind of method that multisection type pack cementation aluminizing prepares composite coating with reference to differential arc oxidation, it is characterised in that including following step
Suddenly：
（1）Pretreatment：It is cleaned by ultrasonic 12～15min with acetone after base material is polished step by step, dries up；
（2）The process of multisection type pack cementation aluminizing：First aluminizing medium is prepared as following weight percent：For aluminium agent 9～11wt% of aluminium powder,
Activator is fluorinated 2～4wt% of sodium powder and filler 86～88wt% of alumina powder, is then mixed using ball mill, then will fully mix
Even aluminizing medium and base material is sealed in together in ceramic crucible, is finally placed in vacuum tube furnace, arrange parameter：Vacuum is
3.5×10-2The heating rate of～7.0Pa, 9～11 DEG C/min rise to 120～150 DEG C insulation 1h, 300 ~ 350 DEG C insulation 2h, 900
～1000 DEG C of 2～6h of insulation, then room temperature is cooled to the furnace to after 400 ~ 500 DEG C with the cooldown rate of 9～11 DEG C/min, obtain
NbAl3The aluminising base material of aluminized coating；
（3）Differential arc oxidation process：From dipulse high voltage power supply as pressure source, aluminising base material is hung on into anode, with stainless
Used as negative electrode, aluminising base material is immersed in electrolyte to steel tank, and compound additive electrolyte is by 10～14g/L of sodium metaaluminate, hydroxide
2～6g/L of sodium, 2～6g/L of sodium fluoride, the g/L of sodium tungstate 4～8,1～3g/L of disodium ethylene diamine tetraacetate, 1～4g/L of yttrium nitrate
Composition；Differential arc oxidation process is carried out using constant voltage mode, electrical quantity is set：360～400V of positive voltage, positive dutycycle 10～20%,
300～500Hz of frequency；And apply mechanical agitation, solution temperature control at 30～35 DEG C, process time be after 20～60min
Aluminising base material plates last layer Al2O3Ceramic membrane, is obtained Al2O3 / NbAl3Composite coating.
2. the method that multisection type pack cementation aluminizing according to claim 1 prepares composite coating with reference to differential arc oxidation, its feature
It is：The base material is niobium or niobium alloy.
3. the method that multisection type pack cementation aluminizing according to claim 1 prepares composite coating with reference to differential arc oxidation, its feature
It is：The NbAl3The thickness of aluminized coating is 50～110 μm, Al2O3The thickness of ceramic membrane is 6～15 μm.
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