EP2855733B1 - Method for coating a substrate containing cobalt, nickel and/or iron with a corrosion-resistant layer - Google Patents
Method for coating a substrate containing cobalt, nickel and/or iron with a corrosion-resistant layer Download PDFInfo
- Publication number
- EP2855733B1 EP2855733B1 EP13734317.4A EP13734317A EP2855733B1 EP 2855733 B1 EP2855733 B1 EP 2855733B1 EP 13734317 A EP13734317 A EP 13734317A EP 2855733 B1 EP2855733 B1 EP 2855733B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- slurry
- substrate
- nickel
- aluminum
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 239000000758 substrate Substances 0.000 title claims description 60
- 238000000034 method Methods 0.000 title claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 48
- 238000000576 coating method Methods 0.000 title claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 38
- 239000011248 coating agent Substances 0.000 title claims description 29
- 229910052759 nickel Inorganic materials 0.000 title claims description 21
- 229910052742 iron Inorganic materials 0.000 title claims description 15
- 230000007797 corrosion Effects 0.000 title claims description 12
- 238000005260 corrosion Methods 0.000 title claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 11
- 229910017052 cobalt Inorganic materials 0.000 title claims description 10
- 239000010941 cobalt Substances 0.000 title claims description 10
- 239000002002 slurry Substances 0.000 claims description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 52
- 229910052782 aluminium Inorganic materials 0.000 claims description 49
- 239000010410 layer Substances 0.000 claims description 38
- 229910000951 Aluminide Inorganic materials 0.000 claims description 18
- 239000002344 surface layer Substances 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkyl phosphates Chemical class 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 159000000032 aromatic acids Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 29
- 230000008569 process Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 18
- 238000009792 diffusion process Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000006698 induction Effects 0.000 description 8
- 238000007581 slurry coating method Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910000943 NiAl Inorganic materials 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910015372 FeAl Inorganic materials 0.000 description 2
- 244000089486 Phragmites australis subsp australis Species 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005552 hardfacing Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
-
- 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
- C23C10/02—Pretreatment of the material to be coated
-
- 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
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
-
- 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
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
- C23C18/10—Deposition of aluminium 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
Definitions
- the invention relates to a process for coating a cobalt-, nickel- and / or iron-containing substrate with a corrosion-resistant layer.
- Substrates such as components and components used at high temperatures, e.g. Plant components in the chemical industry must be protected against corrosion. There is therefore a general need to produce cost-effective and effective coatings for such components and components.
- the most commonly used technique to avoid hot gas corrosion and component oxidation is to apply aluminum-rich topcoats to the substrates, a process called aluminizing.
- aluminizing a process called aluminum-rich topcoats.
- the surfaces of components which are used at high temperatures and which are also exposed to strong corrosion attacks are equipped with conventional aluminide coatings, hardfacing layers or high-alloyed thermal spray coatings.
- Aluminum preferably forms intermetallic compounds with nickel, cobalt and iron.
- the phases with less Al content namely the aluminum-poorer phases NiAl or Co-Al or FeAl, are resistant to the extremely brittle phases such as Fe 14 Al 86 [Xiang et al.] Or Fe 2 Al 5 [Perez et al., Pipe et al.], NiAl 3 or Ni 2 Al 3 or Co 2 Al 5 , because they are less prone to cracking.
- a protective oxide layer which also forms on the aluminum-poor intermetallic compounds, consists of slow-growing, well-adhering and very stable alumina.
- coatings There are two types of coatings: On the one hand, surface coatings applied to the substrate surface and, on the other hand, diffusion coatings produced by diffusing elements such as aluminum, chromium or silicon into the edge zone of the substrate.
- CVD Chemical Vapor Deposition
- a second possibility is the application of aluminum-rich metal (Fe, Ni, Co) chromium-aluminum-yttrium (MCrAlY) overlays.
- These layers are usually applied, for example, by means of build-up welding or thermal spraying. In use, these layers also form protective alumina on the surface. In addition, however, they contain other elements that contribute to the oxidation protection, such as chromium and yttrium. As a result, the aluminum content in these layers may be less than is necessary in diffusion layers. In this way, other alloys can be used be applied to corrosion-prone materials. However, the process is relatively expensive and expensive.
- Slurry coatings are another alternative that is already being used as commercial coatings and that, for example, of Allen et al. US 3,248,251 or Mosser et al. in US 5,650,235 have been described.
- intermetallic coatings are produced by reaction and interdiffusion between the substrate and a metal-containing powder applied to the component surface along with a binder, see e.g. See, for example, Joseph US 3,102,044 .
- the layers produced are similar to those produced by packing methods and, in addition to the elements from the slurry, always contain the elements of the base material due to the high temperature during the interdiffusion step.
- the slurry coatings are also diffused in a diffusion step above 800 ° C.
- this diffusion step which is usually carried out in slurry coating in an inert atmosphere or in a vacuum
- the elements of the base material and the coating diffuse into one another and form not only enriched mixed crystals but also intermetallic compounds.
- the aluminum from the slurry reacts with nickel, cobalt or iron of the base material and forms the desired aluminides.
- Previous methods are limited to nickel, cobalt base materials or austenitic steels, since the temperature treatment above 800 ° C must be carried out because otherwise form on the surface due to the high aluminum supply very aluminum-rich intermetallic brittle phases such as Fe 2 Al 5 or NiAl 3 . For this reason, a coating of ferritic steels with Slurry coatings previously not possible due to the temperature limits for these materials.
- the previously known coatings often contain other elements and components in addition to aluminum in the slurry.
- the best known commercial alloy powder in this field sold under the trade name Serma Loy J by Sermatech Int., USA, consists of 35% Al powder, 6% Si powder, 47% water, and 12% phosphate and chromate containing ties.
- Serma Loy J sold under the trade name Serma Loy J by Sermatech Int., USA
- an eutectic alloy system Al-Si is diffused as a component of the slurry.
- All these coatings are therefore based on the fact that the aluminum atoms of the slurry during the heat treatment with certain elements from the substrate, which have a special affinity for aluminum, to intermetallic compounds. Particularly suitable for this are the substrate components nickel or cobalt, but also iron.
- the US 2 927 043 A discloses a method of coating ferrous components: A slurry of aluminum particles with a flux is applied to the surface of a component, after which the component is heat treated for 5 to 10 minutes at a temperature that avoids stress in the base material of the component. During this process, the flux and the aluminum particles melt, forming a protective aluminum layer.
- the CN 1 397 664 A discloses a member of magnesium coated with aluminum using surface annealing.
- the invention is thus based on the object of representing a cost-effective method for corrosion protection of substrates (components) made of cobalt, nickel and / or iron-containing materials, in which the material and the resulting corrosion protection layers do not tend to form cracks.
- the invention provides that an aluminum-containing slurry is applied to the substrate and the substrate is then subjected to the slurry a short-term temperature-reduced surface annealing.
- the aluminum in the slurry can be in pure form or alloyed, for.
- Under surface annealing should be understood as a heat treatment, which acts essentially on the edge zone of the substrate and therefore only there causes an increase in temperature, while the interior - the body - of the substrate remains substantially unaffected.
- heat treatments are z. B. used for surface hardening of components.
- Short-term means that the surface annealing takes less than 10 minutes.
- Reduced temperature means that the temperature during surface layer annealing in the surface layer and in the slurry is between 550 ° C and 800 ° C.
- the formation of the layer thus takes place not only by interdiffusion with the substrate during a heat treatment of the entire component in the new coating, but by a reaction between the components of the slurry and the nickel of a galvanic layer or the material during a Rander stiirmung and possibly only in the contact zone with the substrate under the nickel plating.
- the invention allows the application of a corrosion protection for steels or nickel alloys which are exposed to a corrosion attack, z. B. in the high temperature range by oxidation, sulfidation or hot gas corrosion.
- the invention is suitable for steels which offer a cost advantage over nickel and cobalt base materials as iron base materials for many applications in the chemical and energy industries.
- the coatings are thus of particular interest for more temperature-sensitive ferritic / martensitic steels, but generally also for components made of austenitic steels, nickel or cobalt-based alloys, since the production costs are significantly lower than those of a complete heat treatment and the parts can be aluminized directly at low cost in air.
- the substrate is heated to a temperature which is above the melting temperature of the aluminum in the slurry.
- Melting temperature of the aluminum refers to the respective appearance of the aluminum (pure or alloyed) in the slurry.
- the duration of the surface layer annealing can be shortened and the process carried out in air, if the slurry contains the aluminum as metal powder with 5-100 ⁇ m particle size, wherein the aluminum can be in pure form, alloyed or as a mixture thereof. Due to the optimized particle size, the aluminum melts in a controlled manner and still reacts easily with the substances in the substrate.
- the surface of the substrate is cleaned prior to application of the slurry.
- the cleaning can preferably be done by sand or shot peening.
- the invention provides that the surface of the substrate before the application of the slurry can be precoated galvanically or by thermal spraying.
- the edge annealing is carried out in vacuo, in an inert gas atmosphere or preferably in air.
- the slurry contains an organic solvent and a binder system which is thermally decomposable.
- the binder system is preferably a synthetic water-soluble or dispersible polymer which does not contain inorganic chromates, phosphates, molybdates or tungstates which are known to be harmful to the environment.
- the binder system contains amphiphiles, low molecular weight phenols, aromatic acids, alkyl phosphates and / or high molecular weight polyelectrolytes.
- the particles of the metal powder are optionally coated with a silicon-containing compound, for. B. with alkoxides, such as tetraethoxysilane as a silicon-containing precursor.
- the substrate is heated to 400 ° C prior to edge annealing, where the aluminide phases forming the coating are formed.
- the metallic powder preferably contains, in addition to the aluminum, at least one of the following elements in the specified maximum contents: Si (10% by mass), Ge (20% by mass), Cr (25% by mass), Ti (2% by mass), Ta, V or Mo (5 mass% each), B (2 mass%), Fe (10 mass%), Co (20 mass%), Ni (30 mass%).
- the slurry contains tin (to 30 mass%), Si (to 10 mass%), Pt (to 10 mass%), Mg (to 20 mass%), Ca (to 20% by mass), one or more elements from the group (lanthanum, cerium, zirconium, hafnium, yttrium) ( ⁇ 1% by mass) or their oxides.
- a proportion of tin in particular allows the use of the invention in metal dusting environments.
- the additives Si, Pt, Mg and Ca and their oxides protect especially from hot gas corrosion.
- the elements of the group (lanthanum, cerium, zirconium, hafnium, yttrium) and their oxides increase the adhesion of oxide layers that form during operation of the components on these.
- the substrate is a steel or a nickel-base alloy or the nickel-plated surface of a component.
- thermochemical diffusion treatment In the heat treatment process, a distinction is made between surface hardening and thermochemical diffusion treatment. In surface hardening, the chemical composition of the surface layer is not changed.
- Surface hardening methods include induction hardening, flame hardening, hardening by means of conductive heating of the surface layer and hardening by means of high-energy heating.
- the invention provides for the use of such a method, but it does not depend on the curing of the surface layer, so that the method in connection with the present invention is also referred to as surface layer annealing.
- a substrate 1 here a tube
- a slurry 2 of aluminum particles on its outer surface.
- the tube is pulled through a coil system 3, inducing electrical currents in the surface of the tube which heat the surface, whereby the slurry 2 converts to an aluminide layer 4 by the reaction excited thereby.
- a substrate 1 here a plate
- a slurry 2 of aluminum particles on its surface.
- One or more burner flames 5 are passed over the surface of the plate, whereby it is heated and the slurry 2 is converted to an aluminide layer 4.
- the surface of the component to be coated is cleaned and freed from dirt and grease.
- the surface can be coated before the coating z. B. blasted with glass beads or sand.
- a slurry is applied to the cleaned surface.
- the binder is preferably an organic polymer, but also silicone-containing binders or additives are conceivable.
- the metal powder in the slurry consists essentially of aluminum or an aluminum alloy. In addition, other alloying elements in elemental or oxidic form may be mixed or alloyed with the aluminum powder.
- the surface can then optionally be galvanically provided with a nickel layer.
- the slurry is applied to the substrate or to the nickel layer and then dried.
- the substrate with the slurry is subjected to an edge-layer annealing in air, in which the reaction between iron / nickel / cobalt and aluminum to aluminides takes place.
- the new coating is more environmentally friendly than conventional coatings, since neither environmentally harmful halides are needed in the production, such.
- chromates or phosphates are still included, as for most conventional slurry coatings, z. From Meelu et. al. in US 6,126,758 respectively. US 5547770 described, needed. In the realization of the new process should even be expressly dispensed with these ingredients.
- the coatings have a homogeneous composition and that the film formation and the connection to the substrate are achieved by an exothermic aluminide formation, which takes place in the temperature range of the melting point of the aluminum alloy.
- an exothermic aluminide formation which takes place in the temperature range of the melting point of the aluminum alloy.
- a heat treatment between 550 ° C and 700 ° C can be generated in this way a layer.
- the minimum necessary temperature for a thin layer is just below or above the melting point of the aluminum powder in the slurry, d. H. the aluminum alloy used.
- a significant advantage of the innovation is that even a short-term, a few minutes lasting surface treatment of the surface layer is sufficient to achieve a coating, in contrast to conventional methods that often require long process times in heat treatment furnaces. Nevertheless, in the layers obtained by the new process, there is sufficient excess aluminum to allow for limited reaction with the substrate, thus ensuring firm bonding of the layer.
- the highlight is the rapid heating in the range between 400 ° C and 700 ° C, whereby a relatively short and local heat treatment, limited to the surface layer, sufficient.
- the metal powder fraction is mixed with binder and solvent, preferably water.
- binder is preferably an organic polymer, but also silicone-containing binders or additives are conceivable.
- the powder in the slurry consists essentially of aluminum or an aluminum alloy. In addition, further alloying elements in elemental or oxidic form may be mixed or alloyed with the aluminum powder or may also be deposited during the galvanic coating step.
- the coated samples were first held at 300 ° C for four hours to burn out the binder.
- reaction step was carried out for coating in laboratory air.
- Example 1 Coating on austenitic iron-based alloy by means of a gas burner
- Fig. 3 The transverse section of an AISI 347 sample can be seen after a flame treatment, as in Fig. 2 shown.
- a short flame reaction time of only five minutes was used to convert the dried and debinded slurry in an area adjoining the substrate into an aluminide diffusion layer 4 by a butane flame as a heat source.
- the layer thickness of the aluminide diffusion layer 4 was already about 25-30 ⁇ m after 5 minutes.
- Example 2 Coating on ferritic iron-based alloy by means of an induction process
- the surface of the component (substrate 1) made of a ferritic P 91 alloy was heated for only two minutes with an induction heating source according to Fig. 1 heated. Since in this case the wall thickness of the component was small (2 mm), the back of the component was also heated to such an extent that a slurry applied there also reacted. As a result, inner surfaces can even be coated by means of the heating according to the invention in the case of thin-walled components.
- the thickness of the aluminide diffusion layer 4 on the substrate P91 in this case is about 60 ⁇ m on the outside (see Fig. 4a ) and about 40-50 ⁇ m on the side facing away from the induction coil (see Fig. 4b ). Again, each remained a residual layer 6 of unconverted slurry.
- Microstructure transformations and changes are suppressed due to the moderate process temperatures ( ⁇ 700 ° C) and times (less than 2 minutes in both examples).
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Description
Die Erfindung bezieht sich auf ein Verfahren zum Beschichten eines kobalt-, nickel- und/oder eisenhaltigen Substrats mit einer korrosionsbeständigen Schicht.The invention relates to a process for coating a cobalt-, nickel- and / or iron-containing substrate with a corrosion-resistant layer.
Substrate, wie Komponenten und Bauteile, die bei hohen Temperaturen eingesetzt werden, z.B. Anlagenteile in der chemischen Industrie, müssen vor Korrosion geschützt werden. Es besteht daher generell das Bedürfnis, kostengünstig und effektiv wirkende Beschichtungen für derartige Komponenten und Bauteile herzustellen.Substrates, such as components and components used at high temperatures, e.g. Plant components in the chemical industry must be protected against corrosion. There is therefore a general need to produce cost-effective and effective coatings for such components and components.
Die am häufigsten angewendete Technik, um Heißgaskorrosion und Oxidation von Bauteilen zu vermeiden, ist das Aufbringen von aluminiumreichen Deckschichten auf die Substrate, ein Prozess, der als Aluminisierung bezeichnet wird. Dazu werden die Oberflächen von Bauteilen, die bei hohen Temperaturen eingesetzt werden und die zugleich starken Korrosionsangriffen ausgesetzt sind, mit konventionellen Aluminidbeschichtungen, Auftragsschweiss-Schichten oder hochlegierten thermischen Spritzschichten ausgerüstet.The most commonly used technique to avoid hot gas corrosion and component oxidation is to apply aluminum-rich topcoats to the substrates, a process called aluminizing. For this purpose, the surfaces of components which are used at high temperatures and which are also exposed to strong corrosion attacks are equipped with conventional aluminide coatings, hardfacing layers or high-alloyed thermal spray coatings.
Aluminium bildet bevorzugt mit Nickel, Kobalt und Eisen intermetallische Verbindungen. Die Phasen mit weniger Al-Anteil, nämlich die aluminiumärmeren Phasen NiAl bzw. Co-Al oder FeAl, sind gegenüber den extrem spröden Phasen wie Fe14Al86 [Xiang et al.] oder Fe2Al5 [Perez et al., Rohr et al.], NiAl3 oder Ni2Al3 bzw. Co2Al5 zu bevorzugen, weil sie weniger anfällig für Rissbildung sind. Eine schützende Oxidschicht, die sich auch auf den aluminiumärmeren intermetallischen Verbindungen ausbildet, besteht aus langsam wachsendem, gut haftendem und sehr stabilem Aluminiumoxid.Aluminum preferably forms intermetallic compounds with nickel, cobalt and iron. The phases with less Al content, namely the aluminum-poorer phases NiAl or Co-Al or FeAl, are resistant to the extremely brittle phases such as Fe 14 Al 86 [Xiang et al.] Or Fe 2 Al 5 [Perez et al., Pipe et al.], NiAl 3 or Ni 2 Al 3 or Co 2 Al 5 , because they are less prone to cracking. A protective oxide layer, which also forms on the aluminum-poor intermetallic compounds, consists of slow-growing, well-adhering and very stable alumina.
Verschiedene Methoden und Beschichtungen, die auf dem Prinzip der Aluminiumanreicherung in der Werkstoffoberfläche beruhen, sind bereits bekannt.Various methods and coatings based on the principle of aluminum enrichment in the material surface are already known.
Dabei sind zwei Arten von Beschichtungen zu unterscheiden: Einerseits Oberflächenbeschichtungen, die auf die Substratoberfläche aufgetragen werden, und andererseits Diffusionsbeschichtungen, die durch Eindiffundieren von Elementen wie Aluminium, Chrom oder Silizium in die Randzone des Substrats entstehen.There are two types of coatings: On the one hand, surface coatings applied to the substrate surface and, on the other hand, diffusion coatings produced by diffusing elements such as aluminum, chromium or silicon into the edge zone of the substrate.
Eine Möglichkeit ist das Chemical Vapour Deposition (CVD)-Verfahren, bei dem Aluminium oder andere Elemente aus der Gasphase mittels Halogenaktivatoren auf der Werkstoffoberfläche abgeschieden werden. Dieses Verfahren ist als "Pack Cementation"-Prozess bekannt und ist in zahlreichen Patenten,
Eine zweite Möglichkeit besteht im Aufbringen von aluminiumreichen Metall (Fe, Ni, Co)-Chrom-Aluminium-Yttrium (MCrAlY)-Auflageschichten. Diese Schichten werden üblicherweise z.B. mittels Auftragsschweißens oder thermischen Spritzens aufgebracht. Im Einsatz bilden diese Schichten ebenfalls an der Oberfläche schützendes Aluminiumoxid aus. Zusätzlich enthalten sie aber weitere Elemente, die zum Oxidationsschutz beitragen, wie z.B. Chrom und Yttrium. Dadurch kann der Aluminiumgehalt in diesen Schichten weniger betragen als in Diffusionsschichten nötig ist. Auf diese Weise können auch andere Legierungen auf korrosionsanfällige Werkstoffe aufgebracht werden. Das Verfahren ist jedoch verhältnismäßig aufwändig und teuer.A second possibility is the application of aluminum-rich metal (Fe, Ni, Co) chromium-aluminum-yttrium (MCrAlY) overlays. These layers are usually applied, for example, by means of build-up welding or thermal spraying. In use, these layers also form protective alumina on the surface. In addition, however, they contain other elements that contribute to the oxidation protection, such as chromium and yttrium. As a result, the aluminum content in these layers may be less than is necessary in diffusion layers. In this way, other alloys can be used be applied to corrosion-prone materials. However, the process is relatively expensive and expensive.
Slurry-Beschichtungen sind eine weitere Alternative, die bereits als kommerzielle Beschichtungen eingesetzt werden und die z.B. von
Wie in den bekannten Pack-Prozessen werden ebenso die Slurry-Coatings bei einem Diffusionsschritt oberhalb von 800°C eindiffundiert. Während dieses Diffusionsschrittes, der bei Slurry-Coating üblicherweise in einer inerten Atmosphäre oder im Vakuum durchgeführt wird, diffundieren die Elemente des Grundwerkstoffes und der Beschichtung ineinander und formen neben angereicherten Mischkristallen auch intermetallische Verbindungen. Insbesondere reagiert das Aluminium aus dem Slurry mit Nickel, Kobalt oder Eisen des Grundwerkstoffs und bildet die gewünschten Aluminide. Bisherige Verfahren sind auf Nickel-, Kobaltbasiswerkstoffe oder austenitischen Stähle beschränkt, da die Temperaturbehandlung oberhalb von 800°C durchgeführt werden muss, weil sich sonst an der Oberfläche durch das hohe Aluminiumangebot sehr aluminiumreiche intermetallische Sprödphasen wie Fe2Al5 oder NiAl3 bilden. Aus diesem Grund ist eine Beschichtung von ferritischen Stählen mit Slurry-Coatings bisher aufgrund der Temperaturgrenzen für diese Werkstoffe nicht möglich.As in the known packing processes, the slurry coatings are also diffused in a diffusion step above 800 ° C. During this diffusion step, which is usually carried out in slurry coating in an inert atmosphere or in a vacuum, the elements of the base material and the coating diffuse into one another and form not only enriched mixed crystals but also intermetallic compounds. In particular, the aluminum from the slurry reacts with nickel, cobalt or iron of the base material and forms the desired aluminides. Previous methods are limited to nickel, cobalt base materials or austenitic steels, since the temperature treatment above 800 ° C must be carried out because otherwise form on the surface due to the high aluminum supply very aluminum-rich intermetallic brittle phases such as Fe 2 Al 5 or NiAl 3 . For this reason, a coating of ferritic steels with Slurry coatings previously not possible due to the temperature limits for these materials.
Die bisher bekannten Beschichtungen enthalten häufig im Slurry neben Aluminium weitere Elemente und Bestandteile. Das bekannteste kommerzielle Legierungspulver in diesem Bereich etwa, das unter dem Markennamen Serma Loy J von der Sermatech Int., USA angeboten wird, besteht aus 35% Al-Pulver, 6% Si-Pulver, 47% Wasser und 12% phosphat- und chromathaltigen Bindern. Eine Weiterentwicklung dieses Beschichtungssystems ist von
Bei allen bisherigen Ansätzen muss jedoch immer das gesamte Bauteil bei Temperaturen größer als 800°C wärmebehandelt werden.In all previous approaches, however, always the entire component at temperatures greater than 800 ° C must be heat treated.
Insbesondere bei Slurry-Coatings, die auf das Aufbringen von Aluminiumlegierungen mittels eines Schlickers oder einer Paste auf die Werkstückoberfläche beruhen, liegen die benötigten Wärmebehandlungstemperaturen jedoch über der typischen Temper-Temperatur von ferritisch-austenitischen Stählen, die max. 650°C beträgt. Ennis et al. zeigten, dass bereits bei 835°C die Kriechfestigkeit dieser Werkstoffe deutlich abnimmt. Dryepondt et al. konnten nachweisen, dass ein CVD-Packprozess bei 1050°C die Korngröße stark erhöht, was sich negativ auf die Risszähigkeit bei niedrigen Temperaturen auswirkt. Trotzdem sind diese Temperaturen bei herkömmlichen Verfahren nötig, da sich sonst durch den hohen Anteil von Aluminium nahe der Oberfläche bei geringer Interdiffusion bevorzugt zunächst die aluminiumreichen, extrem spröden Phasen wie Fe14Al86 [Xiang et al.] oder Fe2Al5 [Perez et al., Rohr et al.] auf Stählen bilden, was zu Rissen führt. Hinzu kommt, dass der thermische Ausdehnungskoeffizient dieser schädlichen Phasen deutlich über demjenigen gängiger Stahl-Werkstoffe liegt und damit die Rissneigung noch verstärkt wird.In particular, in slurry coatings, which are based on the application of aluminum alloys by means of a slurry or a paste on the workpiece surface, however, the required heat treatment temperatures are above the typical annealing temperature of ferritic-austenitic steels, the max. 650 ° C is. Ennis et al. showed that even at 835 ° C, the creep resistance of these materials decreases significantly. Dryepondt et al. could prove that a CVD packing process at 1050 ° C greatly increases the grain size, which has a negative impact on low temperature cracking resistance. Nevertheless, they are These temperatures are necessary in conventional methods, since otherwise due to the high proportion of aluminum near the surface with low interdiffusion preferred initially the aluminum-rich, extremely brittle phases such as Fe 14 Al 86 [Xiang et al.] Or Fe 2 Al 5 [Perez et al ., Rohr et al.] On steels, resulting in cracks. In addition, the thermal expansion coefficient of these harmful phases is significantly higher than that of common steel materials and thus the tendency to crack is even more pronounced.
Bereits bekannt ist, dass durch anschließende Wärmebehandlung bei hohen Temperaturen diese Phasen in die weniger spröden FeAl-Phasen umgewandelt werden können [z.B. Rohr et al.], jedoch sind dann häufig bereits Risse vorhanden, die nicht mehr beseitigt werden können. Zudem wird diese Wärmebehandlung üblicherweise unter Luftausschluss durchgeführt, um die Diffusion zu gewährleisten und den Werkstoffe nicht zu schädigen. Bei niedrigen Temperaturen von beispielsweise 650°c sind dafür mehrere hundert Stunden Auslagerungszeit nötig, was einen erheblichen Nachteil bildet.It is already known that by subsequent heat treatment at high temperatures, these phases can be converted into the less brittle FeAl phases [e.g. Rohr et al.], But then there are often already cracks that can not be eliminated. In addition, this heat treatment is usually carried out under exclusion of air, in order to ensure the diffusion and not to damage the materials. At low temperatures, for example, 650 ° C for several hundred hours Auslagerungszeit are necessary, which is a significant disadvantage.
Die
Die
Die Erfindung beruht somit auf der Aufgabe, eine kostengünstige Methode zu Korrosionsschutz von Substraten (Bauteilen) aus kobalt-, nickel- und/oder eisenhaltigen Werkstoffen darzustellen, bei der der Werkstoff und die entstehenden Korrosionsschutzschichten nicht zu Rissbildungen neigen.The invention is thus based on the object of representing a cost-effective method for corrosion protection of substrates (components) made of cobalt, nickel and / or iron-containing materials, in which the material and the resulting corrosion protection layers do not tend to form cracks.
Zur Lösung der Aufgabe, sieht die Erfindung vor, dass ein Aluminium enthaltender Slurry auf das Substrat aufgebracht wird und das Substrat anschließend mit dem Slurry einem kurzzeitigen temperaturreduzierten Randschichtglühen unterzogen wird.To achieve the object, the invention provides that an aluminum-containing slurry is applied to the substrate and the substrate is then subjected to the slurry a short-term temperature-reduced surface annealing.
Das Aluminium im Slurry kann in Reinform oder legiert, z. B. in Form einer Aluminiumbasislegierung, oder in einer Mischung von reinem oder legiertem Aluminium vorliegen.The aluminum in the slurry can be in pure form or alloyed, for. Example in the form of an aluminum-based alloy, or in a mixture of pure or alloyed aluminum.
Unter Randschichtglühen soll eine Wärmebehandlung verstanden werden, die im Wesentlichen auf die Randzone des Substrats wirkt und daher nur dort eine Temperaturerhöhung bewirkt, während das Innere - der Körper - des Substrats im Wesentlichen unbeeinflusst bleibt. Derartige Wärmebehandlungen werden z. B. zur Randschichthärtung von Bauteilen eingesetzt.Under surface annealing should be understood as a heat treatment, which acts essentially on the edge zone of the substrate and therefore only there causes an increase in temperature, while the interior - the body - of the substrate remains substantially unaffected. Such heat treatments are z. B. used for surface hardening of components.
Kurzzeitig bedeutet, dass das Randschichtglühen weniger als 10 Min. dauert.Short-term means that the surface annealing takes less than 10 minutes.
Temperaturreduziert bedeutet, dass die Temperatur beim Randschichtglühen im der Randschicht und im Slurry zwischen 550°C und 800°C liegt.Reduced temperature means that the temperature during surface layer annealing in the surface layer and in the slurry is between 550 ° C and 800 ° C.
Durch die Erwärmung der Randschicht des Substrats und des Slurrys während des Randschichtglühens findet an der Oberfläche eine exotherme Reaktion zwischen dem Aluminium und dem Substratmetall (Eisen bzw. Nickel) statt, wodurch Aluminidphasen ausgebildet werden, die die Beschichtung bilden.By heating the surface layer of the substrate and the slurry during the surface layer annealing, an exothermic reaction takes place on the surface between the aluminum and the substrate metal (iron or nickel), forming aluminide phases which form the coating.
Damit eröffnet sich die Möglichkeit, z. B. nickelhaltige Substrate mit Aluminid-Beschichtungen für korrosive Bedingungen auszurüsten. Indem ein Verfahren zur Randschichthärtung auf ein Substrat mit aluminiumreichem Slurry angewandt wird, wird erreicht, dass durch eine kurze, wenige Minuten dauernde Wärmebehandlung der Randschicht an Luft das Aluminium aus dem Slurry mit dem galvanischen Nickel aus der Subtratoberfläche reagiert, um auf diese Weise eine Beschichtung zu erzeugen. Dadurch ist die Methode auch hervorragend geeignet, um direkt vor Ort zu beschichten oder um als Reparaturmethode eingesetzt zu werden.This opens up the opportunity z. As nickel-containing substrates with aluminide coatings for corrosive conditions equip. By applying a surface hardening process to a substrate with aluminum-rich slurry, it is achieved that the aluminum from the slurry reacts with the galvanic nickel from the substrate surface for a few minutes of heat treatment of the surface layer in air, thus forming a coating to create. Thereby the method is also excellently suited to coat directly on site or to be used as a repair method.
Als wesentlicher Unterschied zu den im Stand der Technik beschriebenen Diffusionsbeschichtungen findet somit bei der neuen Beschichtung die Ausbildung der Schicht nicht erst durch Interdiffusion mit dem Substrat während einer Wärmebehandlung des gesamten Bauteiles statt, sondern durch eine Reaktion zwischen den Komponenten des Slurrys und dem Nickel einer Galvanikschicht bzw. des Werkstoffes während einer Randerwärmung sowie ggf. nur in der Kontaktzone mit dem Substrat unter der Vernickelung.As an essential difference to the diffusion coatings described in the prior art, the formation of the layer thus takes place not only by interdiffusion with the substrate during a heat treatment of the entire component in the new coating, but by a reaction between the components of the slurry and the nickel of a galvanic layer or the material during a Randerwärmung and possibly only in the contact zone with the substrate under the nickel plating.
Das neue Verfahren bietet viele Vorteile:
- 1.Die Wärmeeinbringung mittels klassischer Methoden der Randschichtwärmebehandlung - wie Flammhärten, Induktionshärten, konduktives Erwärmen mit Heizbändern, Laserstrahl- und Elektronenstrahlhärten - ist möglich.
- 2.Durch das neue Verfahren ist auch eine erste Beschichtung vor Ort in den Anlagen oder Wiederbeschichtung im Rahmen von Wartungsarbeiten möglich.
- 3.Durch die niedrigere Reaktionstemperatur zwischen dem Aluminium aus dem Slurry und dem Nickel in Kombination mit der Verwendung von Randschichtwärmebehandlungsmethoden ist bei entsprechend schneller Aufheizung zwischen 400°C und 700°C ein Prozess an der Luft möglich.
- 4.Durch die exotherme, schnelle Reaktion zwischen Aluminium und Substrat ist es im Gegensatz zu herkömmlichen Diffusionsschichten möglich, auch nichtmetallische Partikel, z.B. Oxide, fein verteilt in die Schichten einzubringen. Dadurch kann z B. die chemische Schichtzusammensetzung für den jeweiligen Beanspruchungsfall optimiert werden oder der thermische Ausdehnungskoeffizient der Schichten dem jeweiligen Substrat angepasst werden.
- 5. Durch die Optimierung der Zusammensetzung des Slurrys und die einfache Möglichkeit, weitere Elemente einzubringen, lässt sich die Entstehung von eisenreichen und aluminiumreichen intermetallischen Verbindungen unterdrücken, die als extrem spröde bekannt sind und bei herkömmlichen Beschichtungen eine hohe Diffusionstemperatur nötig machen, um Rissbildung zu vermeiden.
- 6. Die benötigten Temperaturen und Zeiten der Wärmebehandlung sind deutlich niedriger als bei den herkömmlichen Diffusionsverfahren (<800°C, Sekunden-Minuten statt Stunden).
- 7. Für viele Substrate kann auf eine weitere anschließende thermische Behandlung verzichtet werden, auch um eine übermäßige Interdiffusion mit dem Substrat zu vermeiden.
- 1.The heat input by classical methods of surface layer heat treatment - such as flame hardening, induction hardening, conductive heating with heating tapes, laser beam and electron beam hardening - is possible.
- 2.The new process also makes it possible to carry out an initial on-site coating or re-coating as part of maintenance work.
- 3.Because of the lower reaction temperature between the aluminum from the slurry and the nickel in combination with the use of surface layer heat treatment methods, a process in air is possible with correspondingly rapid heating between 400 ° C and 700 ° C.
- 4.Durch the exothermic, rapid reaction between aluminum and substrate, it is possible in contrast to conventional diffusion layers, even non-metallic particles, such as oxides, finely distributed in the To bring in layers. As a result, it is possible, for example, to optimize the chemical layer composition for the respective load case or to adapt the thermal expansion coefficient of the layers to the respective substrate.
- 5. By optimizing the composition of the slurry and the ease of incorporation of other elements, it is possible to suppress the formation of iron-rich and aluminum-rich intermetallic compounds known as extremely brittle which require a high diffusion temperature in conventional coatings to avoid cracking ,
- 6. The required temperatures and times of the heat treatment are significantly lower than in the conventional diffusion method (<800 ° C, seconds-seconds instead of hours).
- 7. For many substrates, a further subsequent thermal treatment can be dispensed with, also to avoid excessive interdiffusion with the substrate.
Die Erfindung erlaubt die Aufbringung eines Korrosionsschutzes für Stähle oder Nickellegierungen, die einem Korrosionsangriff ausgesetzt sind, z. B. im Hochtemperaturbereich durch Oxidation, Sulfidierung oder Heißgaskorrosion. Bevorzugt ist die Erfindung geeignet für Stähle, die als Eisenbasiswerkstoffe für viele Anwendungen der chemischen Industrie und der Energietechnik einen Kostenvorteil gegenüber Nickel- und Kobaltbasiswerkstoffen bieten.The invention allows the application of a corrosion protection for steels or nickel alloys which are exposed to a corrosion attack, z. B. in the high temperature range by oxidation, sulfidation or hot gas corrosion. Preferably, the invention is suitable for steels which offer a cost advantage over nickel and cobalt base materials as iron base materials for many applications in the chemical and energy industries.
Durch die erfindungsgemäße Vorgehensweise, nämlich nur die Randzone des Substrats zu erwärmen, wird nur die Oberfläche thermisch beansprucht, und das metallische Innere des Substrats bleibt praktisch unverändert. Die Beschichtungen sind damit insbesondere für die temperaturempfindlicheren Ferritisch/Martensitischen Stähle, aber generell auch für Komponenten aus austenitischen Stählen, Nickel- oder Kobaltbasislegierungen interessant, da die Produktionskosten deutlich unter denen einer kompletten Wärmebehandlung liegen und die Teile direkt kostengünstig an Luft aluminisiert werden können.Due to the procedure according to the invention, namely to heat only the edge zone of the substrate, only the surface is subjected to thermal stress, and the metallic interior of the substrate remains virtually unchanged. The coatings are thus of particular interest for more temperature-sensitive ferritic / martensitic steels, but generally also for components made of austenitic steels, nickel or cobalt-based alloys, since the production costs are significantly lower than those of a complete heat treatment and the parts can be aluminized directly at low cost in air.
Um zu erreichen, dass die durch die Wärmebehandlung entstehende Schicht fest am Substrat haftet, wird beim Randschichtglühen das Substrat auf eine Temperatur erhitzt, die über der Schmelztemperatur des Aluminiums im Slurry liegt.In order to ensure that the layer resulting from the heat treatment adheres firmly to the substrate, in the case of surface-layer annealing the substrate is heated to a temperature which is above the melting temperature of the aluminum in the slurry.
Schmelztemperatur des Aluminiums bezieht sich auf die jeweilige Erscheinungsform des Aluminiums (rein oder legiert) im Slurry.Melting temperature of the aluminum refers to the respective appearance of the aluminum (pure or alloyed) in the slurry.
Die Dauer des Randschichtglühens kann verkürzt und der Prozess in Luft durchgeführt werden, wenn der Slurry das Aluminium als Metallpulver mit 5-100 µm Partikelgröße enthält, wobei das Aluminium in Reinform, legiert oder als Mischung davon vorliegen kann. Durch die optimierte Partikelgröße schmilzt das Aluminium kontrolliert und reagiert trotzdem leicht mit den Substanzen im Substrat.The duration of the surface layer annealing can be shortened and the process carried out in air, if the slurry contains the aluminum as metal powder with 5-100 μ m particle size, wherein the aluminum can be in pure form, alloyed or as a mixture thereof. Due to the optimized particle size, the aluminum melts in a controlled manner and still reacts easily with the substances in the substrate.
Die Oberfläche des Substrats wird vor dem Aufbringen des Slurrys gereinigt. Die Reinigung kann vorzugsweise durch Sand- oder Kugelstrahlen erfolgen.The surface of the substrate is cleaned prior to application of the slurry. The cleaning can preferably be done by sand or shot peening.
Weiterhin sieht die Erfindung vor, dass die Oberfläche des Substrats vor dem Aufbringen des Slurrys galvanisch oder mittels thermischen Spritzens vorbeschichtet werden kann.Furthermore, the invention provides that the surface of the substrate before the application of the slurry can be precoated galvanically or by thermal spraying.
Das Randglühen wird im Vakuum, in einer Inertgas-Atmosphäre oder vorzugsweise an Luft durchgeführt.The edge annealing is carried out in vacuo, in an inert gas atmosphere or preferably in air.
Da das Verfahren an der Luft durchgeführt werden kann, ist der apparative Aufwand gering. Es eignet sich daher auch besonders gut, um frei liegende Rohrleitungen in Kraftwerken mit einer Beschichtung zu versehen.Since the process can be carried out in the air, the expenditure on equipment is low. It is therefore particularly well suited to provide exposed pipelines in power plants with a coating.
Um die entstehende Beschichtung zu stabilisieren, ist weiterhin vorgesehen, dass der Slurry ein organisches Lösungsmittel sowie ein Bindersystem enthält, das thermisch zersetzbar ist.In order to stabilize the resulting coating, it is further provided that the slurry contains an organic solvent and a binder system which is thermally decomposable.
Das Bindersystem ist vorzugsweise ein synthetisches wasserlösliches oder dispergierbares Polymer, das keine anorganischen Chromate, Phosphate, Molybdate oder Wolframate enthält, die als umweltschädlich bekannt sind.The binder system is preferably a synthetic water-soluble or dispersible polymer which does not contain inorganic chromates, phosphates, molybdates or tungstates which are known to be harmful to the environment.
Zur Stabilisierung des Alumniumpulvers enthält das Bindersystem Amphiphile, niedrigmolekulare Phenole, aromatische Säuren, oberflächenaktive Alkylphosphate und/oder hochmolekularen Polyelektrolyten.To stabilize the aluminum powder, the binder system contains amphiphiles, low molecular weight phenols, aromatic acids, alkyl phosphates and / or high molecular weight polyelectrolytes.
Weiterhin sind dazu die Partikel des Metallpulvers gegebenenfalls mit einer siliziumhaltigen Verbindung beschichtet, z. B. mit Alkoxiden, wie Tetraethoxysilan als siliziumhaltigen Precursor.Furthermore, the particles of the metal powder are optionally coated with a silicon-containing compound, for. B. with alkoxides, such as tetraethoxysilane as a silicon-containing precursor.
Um organische Anteile auszubrennen, wird das Substrat vor dem Randglühen, bei dem die die Beschichtung bildenden Aluminidphasen ausgebildet werden, bis 400°C erwärmt.In order to burn out organic matter, the substrate is heated to 400 ° C prior to edge annealing, where the aluminide phases forming the coating are formed.
Das metallische Pulver enthält vorzugsweise neben dem Aluminium mindestens eines der folgenden Elemente in den angegebenen Maximalgehalten: Si (10 Massen-%), Ge (20 Massen-%), Cr (25 Massen-%), Ti (2 Massen-%), Ta, V oder Mo (je 5 Massen-%), B (2 Massen-%), Fe (10 Massen-%), Co (20 Massen-%), Ni (30 Massen-%).The metallic powder preferably contains, in addition to the aluminum, at least one of the following elements in the specified maximum contents: Si (10% by mass), Ge (20% by mass), Cr (25% by mass), Ti (2% by mass), Ta, V or Mo (5 mass% each), B (2 mass%), Fe (10 mass%), Co (20 mass%), Ni (30 mass%).
Um ein eine verbesserte Oxidschichthaftung zu erreichen, enthält der Slurry Zinn (bis 30 Massen-%), Si (bis 10 Massen-%), Pt (bis 10 Massen-%), Mg (bis 20 Massen-%), Ca (bis 20 Massen-%), ein oder mehrere Elemente aus der Gruppe (Lanthan, Cer, Zirkonium, Hafnium, Yttrium) (<1 Massen-%) oder deren Oxide.In order to achieve improved oxide layer adhesion, the slurry contains tin (to 30 mass%), Si (to 10 mass%), Pt (to 10 mass%), Mg (to 20 mass%), Ca (to 20% by mass), one or more elements from the group (lanthanum, cerium, zirconium, hafnium, yttrium) (<1% by mass) or their oxides.
Ein Anteil von Zinn erlaubt insbesondere den Einsatz der Erfindung in Metal-Dusting-Umgebungen. Die Zusätze Si, Pt, Mg und Ca und deren Oxide schützen insbesondere vor Heißgaskorrosion.A proportion of tin in particular allows the use of the invention in metal dusting environments. The additives Si, Pt, Mg and Ca and their oxides protect especially from hot gas corrosion.
Die Elemente aus der Gruppe (Lanthan, Cer, Zirkonium, Hafnium, Yttrium) und deren Oxide erhöhen die Haftung von Oxidschichten, die sich im Betrieb der Bauteile auf diesen ausbilden.The elements of the group (lanthanum, cerium, zirconium, hafnium, yttrium) and their oxides increase the adhesion of oxide layers that form during operation of the components on these.
Vorzugsweise ist das Substrat ein Stahl oder eine Nickelbasislegierung oder die vernickelte Oberfläche eines Bauteils.Preferably, the substrate is a steel or a nickel-base alloy or the nickel-plated surface of a component.
Im Folgenden soll anhand eines Ausführungsbeispieles die Erfindung näher erläutert werden. Dazu zeigen:
- Fig. 1
- die schematische Darstellung einer Vorrichtung zum Induktionshärten, mit der das erfindungsgemäße Verfahren durchgeführt werden kann,
- Fig. 2
- die schematische Darstellung einer Vorrichtung zum Flammhärten, mit der das erfindungsgemäße Verfahren ebenfalls durchgeführt werden kann,
- Fig. 3
- einen Querschliff durch die Beschichtung eines authentischen Stahles nach der Durchführung des erfindungsgemäßen Verfahrens mittels Brennerbeflammung gemäß
Fig. 2 , - Fig. 4a
- einen Querschliff durch die Außenbeschichtung eines Rohres aus authentischem Stahl und
- Fig. 4b
- einen Querschliff durch die Innenbeschichtung eines Rohres aus authentischem Stahl nach der Durchführung des erfindungsgemäßen Verfahrens mittels Induktion gemäß
Fig. 1 .
- Fig. 1
- the schematic representation of an apparatus for induction hardening, with which the method according to the invention can be carried out,
- Fig. 2
- the schematic representation of a device for flame hardening, with the method of the invention can also be carried out,
- Fig. 3
- a cross section through the coating of an authentic steel after carrying out the method according to the invention by means of burner flame according to
Fig. 2 . - Fig. 4a
- a cross section through the outer coating of a tube of authentic steel and
- Fig. 4b
- a transverse section through the inner coating of a tube of authentic steel after the implementation of the method according to the invention by means of induction according to
Fig. 1 ,
Beim Wärmebehandlungsverfahren wird zwischen Randschichthärten und thermochemischer Diffusionsbehandlung unterschieden. Beim Randschichthärten wird die chemische Zusammensetzung der Randschicht nicht verändert. Verfahren zum Randschichthärten sind: Induktionshärten, Flammhärten, Härten mittels konduktiver Erwärmung der Randschicht und Härten mittels Hochenergieerwärmung.In the heat treatment process, a distinction is made between surface hardening and thermochemical diffusion treatment. In surface hardening, the chemical composition of the surface layer is not changed. Surface hardening methods include induction hardening, flame hardening, hardening by means of conductive heating of the surface layer and hardening by means of high-energy heating.
Die Erfindung sieht die Anwendung eines solchen Verfahrens vor, wobei es aber nicht auf die Härtung der Randschicht ankommt, so dass das Verfahren in Zusammenhang mit der vorliegenden Erfindung auch als Randschichtglühen bezeichnet wird.The invention provides for the use of such a method, but it does not depend on the curing of the surface layer, so that the method in connection with the present invention is also referred to as surface layer annealing.
In der
In der
Um eine aluminiumreiche Beschichtung auf Eisen-, Nickel- oder Kobaltbasislegierungen auf die Oberfläche eines Bauteils aufzubringen, wird zunächst die Oberfläche des zu beschichtenden Bauteils gesäubert und von Schmutz und Fetten befreit. Die Oberfläche kann dazu zusätzlich vor der Beschichtung z. B. mit Glasperlen oder Sand gestrahlt werden.In order to apply an aluminum-rich coating on iron, nickel or cobalt-based alloys to the surface of a component, first the surface of the component to be coated is cleaned and freed from dirt and grease. In addition, the surface can be coated before the coating z. B. blasted with glass beads or sand.
Auf die gereinigte Oberfläche wird ein Slurry aufgebracht. Dazu wird ein Metallpulver mit Binder und Lösungsmittel, bevorzugt Wasser, gemischt. Der Binder ist vorzugsweise ein organisches Polymer, aber auch silikonhaltige Binder oder Zusätze sind denkbar. Das Metallpulver im Slurry besteht im Wesentlichen aus Aluminium oder einer Aluminiumlegierung. Daneben können weitere Legierungselemente in elementarer oder oxidischer Form dem Aluminiumpulver beigemischt oder zulegiert sein.A slurry is applied to the cleaned surface. For this purpose, a metal powder with binder and solvent, preferably water, mixed. The binder is preferably an organic polymer, but also silicone-containing binders or additives are conceivable. The metal powder in the slurry consists essentially of aluminum or an aluminum alloy. In addition, other alloying elements in elemental or oxidic form may be mixed or alloyed with the aluminum powder.
Die Oberfläche kann danach optional galvanisch mit einer Nickelschicht versehen werden.The surface can then optionally be galvanically provided with a nickel layer.
Der Slurry wird auf das Substrat beziehungsweise auf die Nickelschicht aufgebracht und danach getrocknet.The slurry is applied to the substrate or to the nickel layer and then dried.
Danach werden zunächst in einem Temperaturbereich zwischen 150°C und 400°C die organischen Bestandteile des Slurrys ausgebrannt.Thereafter, first in a temperature range between 150 ° C and 400 ° C, the organic components of the slurry are burned out.
Wenn das erfolgt ist, wird das Substrat mit dem Slurry einem Randschichtglühen an Luft unterzogen, bei dem die Reaktion zwischen Eisen/Nickel/Kobalt und Aluminium zu Aluminiden stattfindet.When this is done, the substrate with the slurry is subjected to an edge-layer annealing in air, in which the reaction between iron / nickel / cobalt and aluminum to aluminides takes place.
Beim raschem Erwärmen auf Temperaturen zwischen 550°C und 700°C kommt es beim Übersteigen der Schmelztemperatur der Aluminiumlegierung des Metallpulvers im Slurry an der Oberfläche des Substrates zu einer Reaktion mit dem Grundwerkstoff und damit zu einer chemischen Anbindung der Schicht an das Substrat. Eine Aluminidbildung erfolgt nach wenigen Sekunden; die Beschichtungszone und die Interdiffusionszone sind deutlich dünner als bei herkömmlichen Beschichtungen (ca. 20-80 µm).Upon rapid heating to temperatures between 550 ° C and 700 ° C occurs when exceeding the melting temperature of the aluminum alloy of the metal powder in the slurry at the surface of the substrate to a reaction with the base material and thus to a chemical bonding of the layer to the substrate. Aluminide formation takes place after a few seconds; the coating zone and the inter-diffusion zone are significantly thinner than conventional coatings (about 20-80 μ m).
Danach kann eine weitere Wärmebehandlung erfolgen.Thereafter, a further heat treatment can take place.
Indem die eisen- bzw. nickel- oder kobaltreichen Oberflächenbereiche des zu beschichtenden Substrats mit Aluminium aus einer Slurry-Beschichtung zu Aluminiden reagieren, ist es möglich, nahezu rissfreie Beschichtungen bei deutlich niedrigeren Werkstückkerntemperaturen zu erzeugen, als das bisher möglich war. Daneben ist die neue Beschichtung umweltfreundlicher als herkömmliche Coatings, da weder umweltschädliche Halogenide in der Herstellung benötigt werden, wie z. B. beim Verfahren der Packzementation, noch Chromate oder Phosphate enthalten sind, wie sie für die meisten herkömmlichen Slurry-Coatings, z. B. von Meelu et. al. in
Durch eine zusätzliche Verwendung der galvanischen Nickelbeschichtung oder durch zusätzliche Elemente im Slurry kann die Entstehung der sehr eisenreichen Aluminid-Sprödphasen eingeschränkt werden. Im Laufe der Untersuchungen zum Konzept dieser Erfindung wurden etliche Vorteile in der Prozessführung gegenüber herkömmlichen Slurry-Coatings gefunden, die nicht nur eine einfachere und billigere Produktion ermöglichen, sondern daneben auch zu verbesserten Eigenschaften der Beschichtungen führen. Diese werden im Folgenden beschrieben.By additional use of the galvanic nickel coating or by additional elements in the slurry the formation of the very iron-rich aluminide brittle phases can be restricted. In the course of the investigations into the concept of this invention, several advantages have been found in the process control over conventional slurry coatings, which not only allow easier and cheaper production, but also lead to improved properties of the coatings. These are described below.
Ein weiterer wichtiger Punkt ist, dass die Beschichtungen eine homogene Zusammensetzung aufweisen und dass die Schichtbildung und die Anbindung an das Substrat durch eine exotherme Aluminidbildung erzielt werden, die im Temperaturbereich des Schmelzpunktes der Aluminiumlegierung stattfindet. Bereits durch eine Wärmebehandlung zwischen 550°C und 700°C kann auf diese Weise eine Schicht erzeugt werden. Die minimal nötige Temperatur für eine dünne Schicht liegt knapp unter bzw. über dem Schmelzpunkt des Aluminiumpulvers im Slurry, d. h. der verwendeten Aluminiumlegierung.Another important point is that the coatings have a homogeneous composition and that the film formation and the connection to the substrate are achieved by an exothermic aluminide formation, which takes place in the temperature range of the melting point of the aluminum alloy. Already by a heat treatment between 550 ° C and 700 ° C can be generated in this way a layer. The minimum necessary temperature for a thin layer is just below or above the melting point of the aluminum powder in the slurry, d. H. the aluminum alloy used.
Als wesentlicher Vorteil der Neuerung ist zu nennen, dass bereits eine kurzzeitige, wenige Minuten dauernde Temperaturbehandlung der Randschicht ausreicht, um eine Beschichtung zu erzielen, im Gegensatz zu herkömmlichen Verfahren, die häufig lange Prozesszeiten in Wärmebehandlungsöfen benötigen. Dennoch ist in den mittels des neuen Verfahrens erzielten Schichten genügend Aluminiumüberschuss vorhanden, um eine begrenzte Reaktion mit dem Substrat zu ermöglichen und so eine feste Anbindung der Schicht zu gewährleisten. Herauszuheben ist das schnelle Aufheizen im Bereich zwischen 400°C und 700°C, wodurch eine relativ kurze und lokale Wärmebehandlung, begrenzt auf die Randschicht, ausreicht.A significant advantage of the innovation is that even a short-term, a few minutes lasting surface treatment of the surface layer is sufficient to achieve a coating, in contrast to conventional methods that often require long process times in heat treatment furnaces. Nevertheless, in the layers obtained by the new process, there is sufficient excess aluminum to allow for limited reaction with the substrate, thus ensuring firm bonding of the layer. The highlight is the rapid heating in the range between 400 ° C and 700 ° C, whereby a relatively short and local heat treatment, limited to the surface layer, sufficient.
Für den Slurry wird die Metallpulverfraktion mit Binder und Lösungsmittel, bevorzugt Wasser, gemischt. Der Binder ist vorzugsweise ein organisches Polymer, aber auch silikonhaltige Binder oder Zusätze sind denkbar. Das Pulver im Slurry besteht im Wesentlichen aus Aluminium oder einer Aluminiumlegierung. Daneben können weitere Legierungselemente in elementarer oder oxidischer Form dem Aluminiumpulver beigemischt oder zulegiert sein oder während des galvanischen Beschichtungsschrittes mit abgeschieden werden.For the slurry, the metal powder fraction is mixed with binder and solvent, preferably water. The binder is preferably an organic polymer, but also silicone-containing binders or additives are conceivable. The powder in the slurry consists essentially of aluminum or an aluminum alloy. In addition, further alloying elements in elemental or oxidic form may be mixed or alloyed with the aluminum powder or may also be deposited during the galvanic coating step.
Für viele Substrate kann auf eine weitere anschließende thermische Behandlung verzichtet werden, auch um eine übermäßige Interdiffusion mit dem Substrat zu vermeiden.For many substrates can be dispensed with a further subsequent thermal treatment, also to avoid excessive interdiffusion with the substrate.
Proben aus der austenitischen AISI 347-und der ferritischen P 91-Legierung wurden kugelgestrahlt und anschließend mit Ethanol oberflächengereinigt. Anschließend wurde der wasserbasierte Slurry, der Polyvinylalkohol als Binder enthält, mittels "Air Brush-Spraying" aufgetragen. Der Slurry enthielt sphärische Al-Partikel im Größenbereich 2-20 µm. Die aufgetragene Menge betrug ungefähr 12 mg/cm2 . Samples of the austenitic AISI 347 and ferritic P 91 alloys were shot peened and then surface cleaned with ethanol. Subsequently, the water-based slurry containing polyvinyl alcohol as a binder was applied by "Air Brush Spraying". The slurry contained spherical Al particles in the size range 2-20 μ m. The applied amount was about 12 mg / cm 2 .
Die beschichteten Proben wurden zunächst für vier Stunden bei 300°C gehalten, um den Binder auszubrennen.The coated samples were first held at 300 ° C for four hours to burn out the binder.
Nach dem Ausbrennen wurde der Reaktionsschritt zur Beschichtung in Laborluft durchgeführt.After burnout, the reaction step was carried out for coating in laboratory air.
In
In diesem Fall wurde zur Wärmebehandlung die Oberfläche des Bauteils (Substrat 1) aus einer ferritischen P 91-Legierung für nur zwei Minuten mit einer Induktionsheizquelle gemäß
Gefügeumwandlungen und Veränderungen werden aufgrund der moderaten Prozesstemperaturen (<700°C) und -zeiten (in beiden Beispiele weniger als 2 Minuten) unterdrückt.Microstructure transformations and changes are suppressed due to the moderate process temperatures (<700 ° C) and times (less than 2 minutes in both examples).
- 11
- Substratsubstratum
- 22
- Slurryslurry
- 33
- Spulensystemcoil system
- 44
- Aluminidschichtaluminide
- 55
- Brennerflammenburner flames
- 66
- Restschichtresidual layer
Claims (14)
- A method for coating a substrate that contains cobalt, nickel and/or iron with a corrosion-resistant layer, wherein a slurry containing aluminium is applied to the substrate, and the substrate together with the slurry is then subjected to an annealing of the surface layer, which lasts less than 10 min, while the temperature in the surface layer and in the slurry lies between 550 and 800 °C.
- The method according to claim 1, wherein during the annealing of the surface layer, the substrate is heated to a temperature that is above the melting point of the aluminium in the slurry.
- The method according to claim 1 or 2, wherein the slurry contains the aluminium as a metal powder having a particle size of 5-100 µm.
- The method according to any one of the preceding claims, wherein the surface of the substrate is cleaned before the slurry is applied.
- The method according to any one of the preceding claims, wherein the surface of the substrate is precoated galvanically or by thermal spraying before the slurry is applied.
- The method according to any one of the preceding claims, wherein the surface annealing is carried out in a vacuum, in an inert gas atmosphere or in the open air.
- The method according to any one of the preceding claims, wherein the slurry contains an organic solvent and a binder system which can be thermally decomposed.
- The method according to claim 7, wherein the binder system is a synthetic, water-soluble or dispersible polymer that does not contain any inorganic chromates, phosphates, molybdates or wolframates.
- The method according to claim 7 or 8, wherein the binder system contains amphiphiles, low-molecular phenols, aromatic acids, surface-active alkyl phosphates and/or high-molecular polyelectrolytes.
- The method according to any one of the preceding claims, wherein the particles of the metal powder are coated with a silicon-containing compound, e.g. with alkoxides, such as tetrathoxysilane as a silicon-containing precursor.
- The method according to any one of the preceding claims, wherein prior to the surface annealing, in which the aluminide phases that form the coating are formed, the substrate is heated to 400 °C.
- The method according to any one of the preceding claims, wherein the metallic powder contains at least one of the following elements in the indicated maximum concentrations: Si (10 wt %), Ge (20 wt %), Cr (25 wt %), Ti (2 wt %), Ta, V or Mo (5 wt % each), B (2 wt %), Fe (10 wt %), Co (20 wt %) and Ni (30 wit %).
- The method according to any one of the preceding claims, wherein the substrate or the slurry contains tin (up to 30 wt %), Si (up to 10 wt %), Pt (up to 10 wt %), Mg (up to 20 wt %), Ca (up to 20 wt %) and additionally one or more elements from the group comprising: lanthanum, cerium, zirconium, hafnium and yttrium or oxides thereof (<1 wt %).
- The method according to any one of the preceding claims, wherein the substrate is a steel or a nickel-based alloy, or in that the substrate is a nickel-plated surface of a component.
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DE102012010602A DE102012010602A1 (en) | 2012-05-30 | 2012-05-30 | Process for coating a cobalt, nickel and / or iron containing substrate with a corrosion resistant layer |
PCT/DE2013/000295 WO2013178216A1 (en) | 2012-05-30 | 2013-05-29 | Method for coating a substrate containing cobalt, nickel and/or iron with a corrosion-resistant layer |
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WO2023217326A1 (en) * | 2022-05-13 | 2023-11-16 | Dechema-Forschungsinstitut Stiftung Bürgerlichen Rechts | Method for diffusion coating with a cr-si-containing slip |
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WO2018213441A1 (en) * | 2017-05-18 | 2018-11-22 | Magna International Inc. | Coating for steel, coated steel and a method of the same |
WO2020023863A1 (en) * | 2018-07-27 | 2020-01-30 | Magna International Inc. | Method for low cost joining of high pressure die cast aluminum |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2927043A (en) * | 1957-02-20 | 1960-03-01 | Solar Aircraft Co | Aluminum coating processes and compositions |
US3102044A (en) | 1960-09-12 | 1963-08-27 | United Aircraft Corp | Applying protective coating from powdered material utilizing high temperature and low pressure |
US3248251A (en) | 1963-06-28 | 1966-04-26 | Teleflex Inc | Inorganic coating and bonding composition |
US3257230A (en) | 1964-03-24 | 1966-06-21 | Chromalloy American Corp | Diffusion coating for metals |
US3544348A (en) | 1968-10-25 | 1970-12-01 | United Aircraft Corp | Overhaul process for aluminide coated gas turbine engine components |
US4228203A (en) * | 1978-01-27 | 1980-10-14 | Toyo Kogyo Co., Ltd. | Method of forming aluminum coating layer on ferrous base alloy workpiece |
JPH02282465A (en) * | 1989-04-24 | 1990-11-20 | Mazda Motor Corp | Production of sliding member |
GB9210683D0 (en) | 1992-05-19 | 1992-07-08 | Rolls Royce Plc | Multiplex aluminide-silicide coating |
US5795659A (en) | 1992-09-05 | 1998-08-18 | International Inc. | Aluminide-silicide coatings coated products |
US5650235A (en) | 1994-02-28 | 1997-07-22 | Sermatech International, Inc. | Platinum enriched, silicon-modified corrosion resistant aluminide coating |
US6485780B1 (en) * | 1999-08-23 | 2002-11-26 | General Electric Company | Method for applying coatings on substrates |
US6395406B1 (en) * | 2000-04-24 | 2002-05-28 | General Electric Company | Methods for preparing and applying coatings on metal-based substrates, and related compositions and articles |
US6428630B1 (en) * | 2000-05-18 | 2002-08-06 | Sermatech International, Inc. | Method for coating and protecting a substrate |
CN1236105C (en) * | 2002-06-24 | 2006-01-11 | 西安交通大学 | Induction heating method for alloying surface of Mg alloy |
US7270852B2 (en) * | 2003-08-04 | 2007-09-18 | General Electric Company | Aluminizing slurry compositions free of hexavalent chromium, and related methods and articles |
US7390534B2 (en) * | 2003-10-31 | 2008-06-24 | General Electric Company | Diffusion coating process |
US7597934B2 (en) * | 2006-02-21 | 2009-10-06 | General Electric Company | Corrosion coating for turbine blade environmental protection |
JP5403881B2 (en) * | 2007-07-10 | 2014-01-29 | ゼネラル・エレクトリック・カンパニイ | Aluminizing method of serpentine cooling passage of jet engine blade |
WO2010134917A1 (en) * | 2009-05-21 | 2010-11-25 | General Electric Company | Corrosion resistant articles |
SG173932A1 (en) * | 2010-02-25 | 2011-09-29 | United Technologies Corp | Repair of a coating on a turbine component |
-
2012
- 2012-05-30 DE DE102012010602A patent/DE102012010602A1/en not_active Withdrawn
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2013
- 2013-05-29 EP EP13734317.4A patent/EP2855733B1/en not_active Not-in-force
- 2013-05-29 DE DE112013002721.6T patent/DE112013002721A5/en not_active Withdrawn
- 2013-05-29 WO PCT/DE2013/000295 patent/WO2013178216A1/en active Application Filing
- 2013-05-29 US US14/404,377 patent/US20150203952A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023217326A1 (en) * | 2022-05-13 | 2023-11-16 | Dechema-Forschungsinstitut Stiftung Bürgerlichen Rechts | Method for diffusion coating with a cr-si-containing slip |
Also Published As
Publication number | Publication date |
---|---|
US20150203952A1 (en) | 2015-07-23 |
DE112013002721A5 (en) | 2015-02-26 |
DE102012010602A1 (en) | 2013-12-05 |
WO2013178216A1 (en) | 2013-12-05 |
EP2855733A1 (en) | 2015-04-08 |
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