EP3064613B1 - Layered coating system having improved corrosion and wear resistance - Google Patents
Layered coating system having improved corrosion and wear resistance Download PDFInfo
- Publication number
- EP3064613B1 EP3064613B1 EP15157442.3A EP15157442A EP3064613B1 EP 3064613 B1 EP3064613 B1 EP 3064613B1 EP 15157442 A EP15157442 A EP 15157442A EP 3064613 B1 EP3064613 B1 EP 3064613B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- tin
- deposited
- coating
- particles
- 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.)
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- 238000000576 coating method Methods 0.000 title claims description 56
- 239000011248 coating agent Substances 0.000 title claims description 47
- 238000005260 corrosion Methods 0.000 title claims description 35
- 230000007797 corrosion Effects 0.000 title claims description 34
- 239000000758 substrate Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 claims description 27
- 229910000906 Bronze Inorganic materials 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010974 bronze Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 17
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052580 B4C Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 150000001639 boron compounds Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 239000013535 sea water Substances 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 125
- 239000011135 tin Substances 0.000 description 25
- 238000000151 deposition Methods 0.000 description 24
- 239000003792 electrolyte Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910000897 Babbitt (metal) Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910017132 AlSn Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DYHPIVADFQHIQZ-UHFFFAOYSA-N [Ni].[Sb].[Sn] Chemical compound [Ni].[Sb].[Sn] DYHPIVADFQHIQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 boron carbides Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 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 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/021—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 only coatings only including layers of metallic material including 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/027—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 only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
Definitions
- the present invention relates to a layer system comprising a substrate and a coating for a substrate surface for the purpose of corrosion and wear protection, the coating consisting of a first layer deposited on the substrate surface and a second layer deposited on the first layer, wherein the first layer is a bronze Alloy layer consisting of a binary copper-tin-bronze.
- the substrates to be coated may be conductive, metallic components as well as non-conductive substrates such as plastic components.
- the deposited metal layers can on the one hand functionally change the substrate surfaces, on the other hand decorative. While the decorative coating of substrate surfaces is usually directed only to the visual impression of the deposited metal layers, in the field of functional deposition of metal layers, a change in the mechanical and / or chemical surface properties of the substrates is intended.
- the abrasion resistance, wear resistance, surface hardness, the scratch behavior or the corrosion resistance of the surface of the substrate can be changed by deposition of suitable layers.
- both the electrolytic deposition of layers, as well as the autocatalytic deposition of layers is known here.
- chromium layers which are used as a coating for metal surfaces in order to improve the metal surfaces, in particular with regard to their wear resistance and corrosion resistance.
- the electrolytic deposition of hard chromium layers from corresponding chromium electrolytes on metal surfaces is known, wherein the resulting hard chromium coating usually has a greater hardness than the material from which the substrate to be coated is manufactured.
- These layers are also characterized by good corrosion resistance, compared to non-chloride media.
- Hard chrome coatings are used, for example, in the field of design engineering for hydraulic components such as hydraulic cylinders and hydraulic pistons, for pressure rollers in the field of printing technology, or in the field of engine construction, for example for the coating of valve stems.
- a further disadvantage of the hard chrome layers known from the prior art is that they are usually deposited from chromium (VI) -containing electrolytes.
- chromium (VI) is suspected of being carcinogenic and the use of chromium (VI) -containing electrolytes should therefore be avoided.
- EP 0 672 763 B1 a method of coating a metal surface in which a nickel-phosphorus alloy layer is deposited on the metal surface in a first step, to which then a silicon layer is deposited in a vacuum chamber using an ion beam.
- a method for producing a layer system which preferably has a first Layer of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium or magnesium or an alloy of at least one of these metals.
- Deposited on the first layer is preferably a metal-nickel alloy layer, wherein the metal is selected from the group consisting of tin, copper, iron, tungsten and cobalt or an alloy of one of these components. While this coating system has been proven in practice, there is still interest in further improving corrosion resistance and wear resistance.
- a sliding layer for a multi-layer sliding bearing of a tin-based alloy known.
- This may contain, in addition to tin, at least one further element of the group antimony and copper, optionally lead and / or bismuth, and optionally at least one element of the group zirconium, silicon, zinc, nickel and silver.
- Base alloys of the composition SnSbCu and SnSbCuBi are preferred.
- Zirconium and silicon can be present as particles of the form ZrO 2 or SiC in the base alloy. This overlay can be deposited with layer thicknesses between 100 and 400 microns on a bronze layer.
- the WO 88/00251 A2 discloses a bearing metal layer based on AlPb, AlSn or CuPb.
- other alloying components such as tin, antimony, bismuth, titanium, boron, silicon, carbon, nickel, selenium, tellurium and cerium may be mixed.
- Preferred bearing metal layers consist of AlPbSiSnCu and AlSn as well as CuPb with Se, Te or Zr additives. Particles of Al 2 O 3 , TiO 2 , Cr 2 O 3 , ZrO 2 , B 4 C, SiC, AIN and Si 3 N 4 may also be added to the bearing metal layer.
- the bearing metal layer may be covered with a lead-tin alloy or lead-tin-antimony alloy lead-in layer.
- metal alloys in particular aluminum bronze, with hard particles of oxides or carbides, in particular Al 2 O 3 , Cr 2 O 5 and Cr 3 C 2 .
- each of the aforementioned layer systems is in need of improvement in terms of its corrosion resistance and / or in terms of its material requirements.
- a coating consisting of a first bronze alloy layer and a second alloy layer deposited thereon of at least tin, nickel and possibly antimony in comparison with the coatings known from the prior art, has outstanding corrosion resistance, scratch resistance and wear resistance having.
- the combination of the individual layers according to the invention according to claim 1 cooperates in synergetic and unpredictable manner, it has been found in particular that the antimony contained in the second layer as an alloy component interacts electrochemically with the bronze layer and in this way for an electrochemical stabilization of the coating according to the invention im concerned.
- the free corrosion potential at the surface is thereby significantly improved and the electrostatic forces of attraction between the individual layers are increased.
- Corresponding corrosion investigations have shown that the individual layers in each case have a significantly lower corrosion resistance than the coating according to the invention.
- mechanical wear tests have shown that the coating according to the invention has both a higher hardness and a better abrasion resistance and scratch behavior than the respective individual layers.
- the substrates coated according to the invention are exposed to an aqueous solution containing iron (III) chloride in accordance with ASTM standard G48 at a temperature of up to 40 ° C. under acidic conditions .
- the coatings according to the invention exhibit superior corrosion resistance of more than 72 hours under these conditions, which satisfies this standard and therefore the coatings according to the invention are seawater-proof, ie seawater-resistant.
- the coating has a total layer thickness of 2 to 150 ⁇ m, preferably 10 to 100 ⁇ m, more preferably 50 to 75 ⁇ m.
- the choice of the layer thickness depends primarily on the field of application of the substrate and the associated requirements in terms of corrosion resistance and wear resistance. Particularly in the field of large-scale suitable large components which are exposed to a relatively large mechanical load, in particular in the offshore extraction of oil, natural gas or wind power or in ocean shipping, total layer thicknesses of 100 to 150 microns are particularly preferred.
- the second alloy layer of at least tin, nickel and antimony has a layer thickness of at least 1 ⁇ m, preferably of at least 5 ⁇ m and more preferably of at least 10 ⁇ m.
- the particular advantage of the coatings of the invention is to be able to achieve excellent corrosion resistance with a comparatively thin layer thickness.
- the layer thickness of the coatings according to the invention can be greater, if necessary in order to be able to withstand other, in particular mechanical effects.
- the layer thickness can also be 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 75 ⁇ m, 100 ⁇ m or even thicker, depending on the application.
- the coating according to the invention has a higher durability and service life for the same layer thickness, which advantageously leads to a lower maintenance and repair expenditure.
- the first layer is a bronze alloy layer.
- the first layer is formed here from a binary copper-tin-bronze.
- Tin bronzes can be divided into wrought alloys and casting alloys based on their tin content. Wrought alloys have a tin content below 9 wt .-%. Cast alloys have a tin content above 9% by weight. Both types of alloys are basically suitable for use as the first layer in the coating of the invention.
- casting alloys with a tin content of at least 9% by weight, more preferably 9 to 13% by weight and more preferably 11% by weight are preferred.
- tin bronzes in general, and in particular binary copper-tin bronzes with such a tin content in conjunction with the second layer according to the invention have particularly good corrosion resistance and wear resistance.
- other copper alloys, commonly referred to as bronzes also fall under the generic term bronze, in particular aluminum bronzes, beryllium bronzes or lead bronzes.
- Such bronzes are also suitable for use as the first layer in a coating not according to the invention.
- aluminum bronze has excellent sea water resistance.
- the second layer of at least tin, nickel and antimony contains at least one further alloying component.
- This is for example a metal from the group copper, iron, tungsten or cobalt. It has been found that the corrosion resistance and the wear resistance can be further improved by the aforementioned components. According to the applicant's current state of knowledge, the synergetic interaction of these components with antimony results in an increase in the electrochemical stabilization of the individual layers of the coating according to the invention.
- the first layer is deposited directly, ie without any intermediate layers on the substrate.
- the second layer is deposited directly, ie without any intermediate layers on the first layer.
- the surface of the second layer facing away from the first layer carries no further layers.
- the coating is one with a two-layered layer system only.
- the coating contains particles which are contained exclusively in the second layer.
- the particles are preferably formed from a material which has a comparatively high hardness. In this way, advantageously, the wear resistance and the scratch behavior of the coating according to the invention can be further improved.
- the particles are boron or boron compounds selected from boron carbide or boron nitride. Applicable but not according to the invention are particles of silicon compounds or titanium compounds.
- Applicable silicon compounds are therefore silicon carbide (SiC) and / or silicon nitride (Si 3 N 4 ).
- Usable titanium compounds are titanium nitride (TiN), titanium carbonitride (Ti (C, N)) and / or titanium aluminum nitride (TiAIN).
- Boron compounds according to the invention are boron carbide (B 4 C) and / or boron nitride, in particular boron nitride (CBN; cubic crystalline boron nitride).
- the coating can basically be applied to any substrate.
- Metal substrates in particular stainless stainless steels, are particularly preferred substrates as the main substrate in the region of the components which are exposed to seawater and are protected particularly well against corrosion and wear by the coating according to the invention.
- the object of the invention is achieved by a method for coating a substrate surface for the purpose of corrosion and abrasion protection according to claim 3 .
- the coating is deposited on the substrate with a total layer thickness of 2 to 150 .mu.m, preferably with 10 to 100 .mu.m, more preferably with 50 to 75 .mu.m.
- a total layer thickness of 2 to 150 .mu.m preferably with 10 to 100 .mu.m, more preferably with 50 to 75 .mu.m.
- the layer thickness can also be deposited, for example, at 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 75 ⁇ m, 100 ⁇ m or even thicker.
- a bronze alloy layer is deposited as the first layer.
- the first layer is deposited here as a binary copper-tin bronze.
- Both wrought alloys and cast alloys can basically be deposited as the first layer of the coating according to the invention.
- casting alloys with a tin content of at least 9% by weight, particularly preferably 9 to 13% by weight and more preferably 11% by weight are preferably deposited.
- other copper alloys commonly referred to as bronzes, such as, in particular, aluminum bronzes, beryllium bronzes or lead bronzes, which fall under the generic term of bronze, can also be deposited as the first layer. Because of its excellent sea water resistance, it is preferred to deposit aluminum bronze as the first layer.
- At least one further alloying component is deposited to form the second layer.
- a metal from the group copper, iron, tungsten or cobalt is used. It has been shown that the Corrosion resistance and wear resistance can be further improved by the aforementioned components.
- particles are introduced into the coating according to the invention, namely exclusively into the second layer.
- the particles are preferably formed from a material which has a comparatively high hardness.
- particles are boron or boron compounds selected from boron carbide or boron nitride.
- Applicable but not according to the invention are particles of silicon compounds or titanium compounds. It has been shown that in particular the carbides and nitrides of the aforementioned elements have particularly advantageous properties in terms of wear resistance.
- Applicable silicon compounds are therefore silicon carbide (SiC) and / or silicon nitride (Si 3 N 4 ).
- titanium compounds are titanium nitride (TiN), titanium carbonitride (Ti (C, N)) and / or titanium aluminum nitride (TiAIN).
- Boron compounds according to the invention are boron carbide (B 4 C) and / or boron nitride, in particular boron nitride (CBN; cubic crystalline boron nitride).
- CBN boron nitride
- all the above-mentioned compounds may be incorporated in the coating alone or in combination with each other.
- the exclusive use of boron carbides has proven to be particularly advantageous.
- the particles are introduced only in the second layer, whereby an optimized compromise between corrosion and wear protection on the one hand and manufacturing costs and manufacturing costs on the other hand can be achieved.
- the deposition of the individual layers of the coating can be carried out in the state-of-the-art electroless or electrolytic manner, depending on the type of layer.
- an electrolytic deposition under application of a suitable deposition voltage between the substrate surface and a counter electrode and using a conventional bronze electrolyte (aqueous, copper and tin-containing electrolyte) is preferred.
- the deposition of the present invention tin-nickel-antimony alloy layer as a second layer can also be electrolytically under application of a Separation voltage between the substrate surface and a suitable counter electrode or carried out autocatalytically using suitable reducing agents.
- the deposition of the particles takes place according to the invention in a dispersion bath. If particles are not to be introduced into the entire coating according to the invention, the deposition of both the first and the second layer is to be carried out in a dispersion bath. If the particles are to be introduced only into one of the two layers, as in the invention exclusively into the second layer, then only the deposition of the corresponding layer into which the particles are to be introduced must take place in a dispersion bath. To form a homogeneous distribution of the particles in the coating, it is preferably provided to distribute the particles homogeneously in the dispersion bath during the deposition process of the respective layer. For this purpose, the introduction of a gas for circulating the electrolyte may preferably be provided.
- the gas is preferably introduced into the dispersion bath from the bottom of the dispersion bath in the form of fine bubbles.
- the bubbles preferably have a diameter in the range 0.5-10 ⁇ m, preferably 0.5-5 ⁇ m. More preferably, the gas is introduced either via nozzles at the bottom of the dispersion bath in this. Alternatively, the gas is introduced directly through a gas-permeable and liquid-tight membrane which forms the bottom of the bath.
- the gas used is preferably a protective gas. This ensures that there are no unwanted side reactions of the gas with the alloying constituents. Protective gas used in particular in the prior art known protective gases such as nitrogen or argon.
- a homogeneous distribution of the particles in the dispersion bath can also be achieved via electrolyte movement.
- stirring devices for an internally induced movement of electrolytes in the dispersion bath can preferably be used for this purpose.
- the electrolyte can also be set in motion by external excitation. This is preferably achieved by a suitable movement of the container of the dispersion bath.
- the layer systems deposited according to the invention are particularly suitable for coating components in the field of hydraulic engineering, such as piston rods, piston tubes, storage rods, lifting cylinders, luffing cylinders, etc., for the Coating of printing rolls in the field of printing technology, for the coating of plant components and components in the field of marine engineering, in particular in the field of shipbuilding and the offshore extraction of wind power, natural gas and crude oil, as well as in the field of engine construction.
- Fig. 1 the inventive method for coating a substrate surface is shown.
- the substrate in this case of stainless steel ordinary steel, is introduced here in a galvanic bath.
- This contains an aqueous electrolyte 2 with a copper source and a tin source.
- a deposition voltage is applied between said surface and a suitable counterelectrode.
- the deposition of a binary copper-tin-bronze layer as a first layer takes place directly on the substrate surface.
- the bronze layer is deposited with a tin content of 11 wt .-%.
- the layer thickness of the bronze layer is on average at 45 microns.
- the substrate coated with the first layer is removed from the galvanic bronze bath, electrolyte residues are removed and introduced into a galvanic dispersion bath.
- the dispersion bath contains an aqueous electrolyte 3 having a nickel source, a tin source and an antimony source.
- a deposition voltage is applied between said surface and a suitable counterelectrode.
- the dispersion bath contains boron carbide particles 4. These are distributed homogeneously in the dispersion bath for proper incorporation into the second layer.
- the container of the dispersion bath is moved continuously.
- the layer thickness of the second alloy layer is on average 45 m.
- the boron carbide particles 4 are introduced into the second layer.
- the introduction of the particles into the second layer is subject to equilibrium. It is therefore necessary to add the particles to the dispersion bath in an amount based on the amount to be introduced. This accelerates both the introduction of the particles into the second layer and increases the absolute amount of the particles introduced. As a consequence, this advantageously leads to an improvement in the corrosion and wear properties of the coating according to the invention.
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Description
Die vorliegende Erfindung betrifft ein Schichtsystem mit einem Substrat und einer Beschichtung für eine Substratoberfläche zum Zwecke des Korrosions- und Verschleißschutzes, die Beschichtung bestehend aus einer auf der Substratoberfläche abgeschiedenen ersten Schicht und einer auf der ersten Schicht abgeschiedenen zweiten Schicht, wobei die erste Schicht eine Bronze-Legierungsschicht bestehend aus einer binären Kupfer-Zinn-Bronze ist.The present invention relates to a layer system comprising a substrate and a coating for a substrate surface for the purpose of corrosion and wear protection, the coating consisting of a first layer deposited on the substrate surface and a second layer deposited on the first layer, wherein the first layer is a bronze Alloy layer consisting of a binary copper-tin-bronze.
Die Abscheidung von Metallschichten oder Metalllegierungsschichten auf der Oberfläche von Substraten ist seit sehr langer Zeit bekannt. Die zu beschichtenden Substrate können hierbei sowohl leitfähige, metallische Bauteile, als auch nicht-leitfähige Substrate wie beispielswiese Kunststoffbauteile sein. Die abgeschiedenen Metallschichten können zum einen die Substratoberflächen funktional verändern, zum anderen dekorativ. Während die dekorative Beschichtung von Substratoberflächen in der Regel lediglich auf den optischen Eindruck der abgeschiedenen Metallschichten gerichtet ist, ist im Bereich der funktionalen Abscheidung von Metallschichten eine Veränderung der mechanischen und/oder chemischen Oberflächeneigenschaften der Substrate beabsichtigt. So kann beispielsweise die Abriebfestigkeit, Verschleißfestigkeit, Oberflächenhärte, das Ritzverhalten oder die Korrosionsbeständigkeit der Oberfläche des Substrates durch Abscheidung geeigneter Schichten verändert werden. Grundsätzlich ist hierbei sowohl die elektrolytische Abscheidung von Schichten, als auch die autokatalytische Abscheidung von Schichten bekannt.The deposition of metal layers or metal alloy layers on the surface of substrates has been known for a very long time. In this case, the substrates to be coated may be conductive, metallic components as well as non-conductive substrates such as plastic components. The deposited metal layers can on the one hand functionally change the substrate surfaces, on the other hand decorative. While the decorative coating of substrate surfaces is usually directed only to the visual impression of the deposited metal layers, in the field of functional deposition of metal layers, a change in the mechanical and / or chemical surface properties of the substrates is intended. Thus, for example, the abrasion resistance, wear resistance, surface hardness, the scratch behavior or the corrosion resistance of the surface of the substrate can be changed by deposition of suitable layers. Basically, both the electrolytic deposition of layers, as well as the autocatalytic deposition of layers is known here.
Eine wichtige Rolle im Bereich der funktionalen Beschichtungen spielen Chromschichten, welche als Beschichtung für Metalloberflächen eingesetzt werden, um die Metalloberflächen insbesondere hinsichtlich ihrer Verschleißfestigkeit und Korrosionsbeständigkeit zu verbessern. So ist beispielsweise die elektrolytische Abscheidung von Hartchromschichten aus entsprechenden Chromelektrolyten auf Metalloberflächen bekannt, wobei die dadurch erhaltene Hartchrombeschichtung in der Regel eine größere Härte als das Material, aus dem das zu beschichtende Substrat gefertigt ist, besitzen. Diese Schichten zeichnen sich darüber hinaus auch durch gute Korrosionsbeständigkeit aus, gegenüber nicht-chloridhaltigen Medien.An important role in the field of functional coatings play chromium layers, which are used as a coating for metal surfaces in order to improve the metal surfaces, in particular with regard to their wear resistance and corrosion resistance. Thus, for example, the electrolytic deposition of hard chromium layers from corresponding chromium electrolytes on metal surfaces is known, wherein the resulting hard chromium coating usually has a greater hardness than the material from which the substrate to be coated is manufactured. These layers are also characterized by good corrosion resistance, compared to non-chloride media.
Hartchrombeschichtungen werden beispielsweise im Bereich der Konstruktionstechnik für Hydraulikbauteile wie beispielsweise Hydraulikzylinder und Hydraulikkolben, für Druckwalzen im Bereich der Druckmaschinentechnik, oder auch im Bereich des Motorenbaus beispielsweise für die Beschichtung von Ventilschäften eingesetzt.Hard chrome coatings are used, for example, in the field of design engineering for hydraulic components such as hydraulic cylinders and hydraulic pistons, for pressure rollers in the field of printing technology, or in the field of engine construction, for example for the coating of valve stems.
Ein weiteres Anwendungsgebiet solcher Beschichtungen ist die korrosionsbeständige Ausrüstung von Bauteilen und Anlagenkomponenten im Bereich der marinen Konstruktionstechnik sowie der Offshore-Technik. Hier führt der ständige Kontakt der Bauteile und Anlagenkomponenten mit Seewasser, welches naturgemäß über einen hohen Chloridgehalt verfügt, zu drastischen korrosiven Angriffen, die es zu vermeiden gilt. Hier hat sich die Verwendung von Hartchromschichten aufgrund der ungenügenden Korrosionsschutzeigenschaften gegenüber Salzwasser nur bedingt als geeignet gezeigt, um die entsprechenden Bauteile und Anlagenkomponenten sowohl hinsichtlich ihrer mechanischen Belastungsanforderungen, als auch hinsichtlich ihrer Korrosionsbeständigkeit geeignet auszurüsten.Another area of application of such coatings is the corrosion-resistant finishing of components and plant components in the field of marine construction technology as well as offshore technology. Here, the constant contact of the components and system components with seawater, which naturally has a high chloride content, leads to drastic corrosive attacks, which must be avoided. Here, the use of hard chrome has shown due to the insufficient anti-corrosion properties against salt water only limited suitable to equip the appropriate components and system components both in terms of their mechanical stress requirements, as well as in terms of their corrosion resistance suitable.
Ein weiterer Nachteil der aus dem Stand der Technik bekannten Hartchromschichten ist es, dass diese in der Regel aus Chrom(VI)-haltigen Elektrolyten abgeschieden werden. Chrom(VI) steht jedoch in Verdacht, kanzerogen zu wirken und der Einsatz von Chrom(VI)-haltigen Elektrolyten sollte daher vermieden werden.A further disadvantage of the hard chrome layers known from the prior art is that they are usually deposited from chromium (VI) -containing electrolytes. However, chromium (VI) is suspected of being carcinogenic and the use of chromium (VI) -containing electrolytes should therefore be avoided.
Im Stand der Technik wurden daher unterschiedliche Ansätze unternommen, um unter Verzicht der Verwendung von Chrom(VI)-haltigen Elektrolyten Schichten mit vergleichbaren mechanischen und chemischen Eigenschaften abzuscheiden. So offenbart beispielsweise das europäische Patent
Ein solches Verfahren ist jedoch sehr kostenintensiv und aufgrund der benötigten Vakuumkammer auch lediglich für entsprechend kleine Bauteile anwendbar.However, such a method is very costly and due to the required vacuum chamber also applicable only for correspondingly small components.
Zur Vermeidung dieser Nachteile ist mit der
Ferner ist aus der
Die
Aus der
Aus der
Jedes der vorgenannten Schichtsysteme ist jedoch hinsichtlich seiner Korrosionsbeständigkeit und/oder hinsichtlich seines Materialbedarf verbesserungswürdig."However, each of the aforementioned layer systems is in need of improvement in terms of its corrosion resistance and / or in terms of its material requirements. "
Es ist daher die Aufgabe der vorliegenden Erfindung, ein Schichtsystem mit einer Beschichtung bereitzustellen, welche unter Vermeidung der Verwendung Chrom(VI)-haltigen Elektrolyten als Substitut für die aus dem Stand der Technik bekannten Hartchromschichten geeignet ist und bei der die Korrosionsbeständigkeit und die Verschleißfestigkeit gegenüber aus dem Stand der Technik bekannten chromlosen Beschichtungen verbessert sowie deren Materialbedarf demgegenüber verringert ist. Des Weiteren ist es die Aufgabe der vorliegenden Erfindung, ein Verfahren zur Abscheidung einer solchen Beschichtung bereitzustellen.It is therefore the object of the present invention to provide a layer system with a coating which, while avoiding the use of chromium (VI) -containing electrolytes, is suitable as a substitute for the hard chrome layers known from the prior art and which contrasts with the corrosion resistance and the wear resistance improved from the prior art known chromeless coatings and their material requirements is reduced in contrast. Furthermore, it is the object of the present invention to provide a method for depositing such a coating.
Gelöst wird diese Aufgabe hinsichtlich des Schichtsystems durch ein eingangs genanntes Schichtsystem, das zusätzlich die kennzeichnenden Merkmale des Patentanspruchs 1 aufweist. This object is achieved with regard to the layer system by an aforementioned layer system, which additionally has the characterizing features of
Es hat sich herausgestellt, dass eine Beschichtung, bestehend aus einer ersten Bronze-Legierungsschicht und einer zweiten, darauf abgeschiedenen Legierungsschicht aus wenigstens Zinn, Nickel und ggf. Antimon im Vergleich mit den aus dem Stand der Technik bekannten Beschichtungen eine herausragende Korrosionsbeständigkeit, Ritzverhalten und Verschleißfestigkeit aufweist. Die Kombination der erfindungsgemäßen Einzelschichten entsprechend dem Anspruch 1 wirkt in synergetischer und nicht vorhersehbarer Weise zusammen, es hat sich insbesondere herausgestellt, dass das in der zweiten Schicht als Legierungskomponente enthaltene Antimon elektrochemisch mit der Bronzeschicht wechselwirkt und auf diesem Wege für eine elektrochemische Stabilisierung der erfindungsgemäßen Beschichtung im sorgt. Das freie Korrosionspotential an der Oberfläche wird hierdurch deutlich verbessert und die elektrostatischen Anziehungskräfte zwischen den Einzelschichten erhöht. Diesbezügliche Korrosionsuntersuchungen haben gezeigt, dass die jeweils einzelnen Schichten eine deutlich geringere Korrosionsbeständigkeit aufweisen, als die erfindungsgemäße Beschichtung. Analog hierzu haben mechanische Verschleißtests ergeben, dass die erfindungsgemäße Beschichtung sowohl eine höhere Härte, als auch eine bessere Abriebbeständigkeit und Ritzverhalten als die jeweiligen Einzelschichten aufweist.It has been found that a coating consisting of a first bronze alloy layer and a second alloy layer deposited thereon of at least tin, nickel and possibly antimony, in comparison with the coatings known from the prior art, has outstanding corrosion resistance, scratch resistance and wear resistance having. The combination of the individual layers according to the invention according to claim 1 cooperates in synergetic and unpredictable manner, it has been found in particular that the antimony contained in the second layer as an alloy component interacts electrochemically with the bronze layer and in this way for an electrochemical stabilization of the coating according to the invention im worried. The free corrosion potential at the surface is thereby significantly improved and the electrostatic forces of attraction between the individual layers are increased. Corresponding corrosion investigations have shown that the individual layers in each case have a significantly lower corrosion resistance than the coating according to the invention. Analogously, mechanical wear tests have shown that the coating according to the invention has both a higher hardness and a better abrasion resistance and scratch behavior than the respective individual layers.
Zur Überprüfung der Korrosionsbeständigkeit der Beschichtung und insbesondere zur Beurteilung der Korrosionsbeständigkeit gegenüber Salzwasser werden die erfindungsgemäß beschichteten Substrate in Übereinstimmung mit der ASTM-Norm G48 bei einer Temperatur von bis zu 40°C unter sauren Bedingungen einer wässrigen, Eisen(III)-chloridhaltigen Lösung ausgesetzt. Die erfindungsgemäßen Beschichtungen zeigen unter diesen Bedingungen eine überragende Korrosionsbeständigkeit von mehr als 72 Stunden, womit dieser Standard erfüllt ist und die erfindungsgemäßen Beschichtungen insofern seewasserfest, das heißt seewasserbeständig sind.To test the corrosion resistance of the coating and in particular to assess the corrosion resistance to salt water, the substrates coated according to the invention are exposed to an aqueous solution containing iron (III) chloride in accordance with ASTM standard G48 at a temperature of up to 40 ° C. under acidic conditions , The coatings according to the invention exhibit superior corrosion resistance of more than 72 hours under these conditions, which satisfies this standard and therefore the coatings according to the invention are seawater-proof, ie seawater-resistant.
In einer bevorzugten Ausführungsform der Erfindung weist die Beschichtung eine Gesamtschichtdicke von 2 bis 150 µm auf, vorzugsweise 10 bis 100 µm, weiter bevorzugt 50 bis 75 µm. Die Wahl der Schichtdicke richtet sich vorrangig nach dem Einsatzgebiet des Substrates und der damit verbundenen Anforderungen hinsichtlich der Korrosionsbeständigkeit und der Verschleißfestigkeit. Insbesondere im Bereich von hochseetauglichen Großbauteilen die einer vergleichsweise großen mechanischen Belastung ausgesetzt sind, wie insbesondere bei der Offshore-Gewinnung von Erdöl, Erdgas oder Windkraft oder auch bei der Hochseeschifffahrt, sind Gesamtschichtdicken von 100 bis 150 µm besonders bevorzugt. Gemäß einem weiteren bevorzugten Merkmal der Erfindung weist die zweite Legierungsschicht aus wenigstens Zinn, Nickel und Antimon eine Schichtdicke von wenigstens 1 µm, vorzugsweise von wenigstens 5 µm und noch bevorzugter von wenigstens 10 µm auf. Untersuchungen haben ergeben, dass eine Schichtdicke von 2 µm ausreichend ist, um die Korrosionsbeständigkeit in Entsprechung der ASTM-Norm G48 zu erzielen. Damit liegt der besondere Vorteil der erfindungsgemäßen Beschichtungen darin, eine hervorragende Korrosionsbeständigkeit bei einer vergleichsweise dünnen Schichtdicke erreichen zu können. Obgleich die nach ASTM-Norm G48 als seewasserfest zu bezeichnende Korrosionsbeständigkeit bereits bei einer Schichtstärke von nur 2 µm erreicht wird, kann die Schichtstärke der erfindungsgemäßen Beschichtungen größer ausfallen, gegebenenfalls um anderen, insbesondere mechanischen Einwirkungen standhalten zu können. So kann die Schichtdicke beispielsweise auch 20 µm, 30 µm, 40 µm, 75 µm, 100 µm oder noch dicker ausfallen, je nach Anwendungsfall. Im Vergleich mit dem aus dem Stand der Technik bekannten Schichtsystem weist die erfindungsgemäße Beschichtung bei gleicher Schichtdicke eine höhere Haltbarkeit und Lebensdauer auf, was vorteilhafterweise zu einem geringeren Wartungs- und Reparaturaufwand führt.In a preferred embodiment of the invention, the coating has a total layer thickness of 2 to 150 μm, preferably 10 to 100 μm, more preferably 50 to 75 μm. The choice of the layer thickness depends primarily on the field of application of the substrate and the associated requirements in terms of corrosion resistance and wear resistance. Particularly in the field of large-scale suitable large components which are exposed to a relatively large mechanical load, in particular in the offshore extraction of oil, natural gas or wind power or in ocean shipping, total layer thicknesses of 100 to 150 microns are particularly preferred. According to a further preferred feature of the invention, the second alloy layer of at least tin, nickel and antimony has a layer thickness of at least 1 μm, preferably of at least 5 μm and more preferably of at least 10 μm. Investigations have shown that a layer thickness of 2 microns is sufficient to achieve the corrosion resistance in accordance with the ASTM G48 standard. Thus, the particular advantage of the coatings of the invention is to be able to achieve excellent corrosion resistance with a comparatively thin layer thickness. Although the corrosion resistance referred to in ASTM standard G48 is already achieved with a layer thickness of only 2 μm, the layer thickness of the coatings according to the invention can be greater, if necessary in order to be able to withstand other, in particular mechanical effects. For example, the layer thickness can also be 20 μm, 30 μm, 40 μm, 75 μm, 100 μm or even thicker, depending on the application. In comparison with the layer system known from the prior art, the coating according to the invention has a higher durability and service life for the same layer thickness, which advantageously leads to a lower maintenance and repair expenditure.
Erfindungsgemäß ist die erste Schicht eine Bronze-Legierungsschicht. Hierunter fallen dem Grunde nach die klassischen binären, ternären, quaternären und höherwertigen Zinnbronzen mit der allgemeinen Summenformel CuaSnb+...Mz. Gemäß der Erfindung ist die erste Schicht hierbei aus einer binären Kupfer-Zinn-Bronze gebildet. Zinnbronzen lassen sich anhand ihres Zinngehalts in Knetlegierungen und Gusslegierungen einteilen. Knetlegierungen haben einen Zinnanteil unterhalb von 9 Gew.-%. Gusslegierungen haben einen Zinnanteil oberhalb von 9 Gew.-%. Beide Legierungstypen sind dem Grunde nach für eine Verwendung als erste Schicht in der erfindungsgemäßen Beschichtung geeignet. Bevorzugt sind jedoch Gusslegierungen mit einem Zinnanteil von wenigstens 9 Gew.-%, besonders bevorzugt sind 9 bis 13 Gew.-% und weiter bevorzugt 11 Gew.-%. Es hat sich gezeigt, dass Zinnbronzen im Allgemeinen und insbesondere binäre Kupfer-Zinn-Bronzen mit einem solchen Zinnanteil in Verbindung mit der erfindungsgemäßen zweiten Schicht besonders gute Korrosionsbeständigkeiten und Verschleißfestigkeiten aufweisen. Neben den klassischen Bronzen fallen ebenfalls andere, gemeinhin als Bronzen bezeichnete Kupferlegierungen unter den Oberbegriff der Bronze, wie insbesondere Aluminiumbronzen, Berylliumbronzen oder Bleibronzen. Solche Bronzen sind ebenfalls für eine Verwendung als erste Schicht in einer nicht erfindungsgemäßen Beschichtung geeignet. Es hat sich insbesondere gezeigt, dass Aluminiumbronze eine exzellente Seewasserbeständigkeit aufweist.According to the invention, the first layer is a bronze alloy layer. This includes the classic binary, ternary, quaternary and higher-value tin bronzes with the general empirical formula Cu a Sn b + ... M z . According to the invention, the first layer is formed here from a binary copper-tin-bronze. Tin bronzes can be divided into wrought alloys and casting alloys based on their tin content. Wrought alloys have a tin content below 9 wt .-%. Cast alloys have a tin content above 9% by weight. Both types of alloys are basically suitable for use as the first layer in the coating of the invention. However, casting alloys with a tin content of at least 9% by weight, more preferably 9 to 13% by weight and more preferably 11% by weight, are preferred. It has been found that tin bronzes in general, and in particular binary copper-tin bronzes with such a tin content in conjunction with the second layer according to the invention have particularly good corrosion resistance and wear resistance. In addition to the classic bronzes, other copper alloys, commonly referred to as bronzes, also fall under the generic term bronze, in particular aluminum bronzes, beryllium bronzes or lead bronzes. Such bronzes are also suitable for use as the first layer in a coating not according to the invention. In particular, it has been found that aluminum bronze has excellent sea water resistance.
Gemäß einem nicht erfindungsgemäßen Merkmal enthält die zweite Schicht aus wenigstens Zinn, Nickel und Antimon wenigstens eine weitere Legierungskomponente. Diese ist beispielsweise ein Metall aus der Gruppe Kupfer, Eisen, Wolfram oder Kobalt. Es hat sich gezeigt, dass die Korrosionsbeständigkeit und die Verschleißfestigkeit durch vorgenannte Komponenten weiter verbessert werden kann. Nach derzeitiger Kenntnislage des Anmelders ergibt sich aus der synergetischen Wechselwirkung dieser Komponenten mit Antimon eine Verstärkung der elektrochemischen Stabilisierung der Einzelschichten der erfindungsgemäßen Beschichtung. Die erste Schicht ist unmittelbar, d.h. ohne etwaige Zwischenschichten auf dem Substrat abgeschieden. Die zweite Schicht ist unmittelbar, d.h. ohne etwaige Zwischenschichten auf der ersten Schicht abgeschieden. Die der ersten Schicht abgewandte Oberfläche der zweiten Schicht trägt keine weiteren Schichten. Besagte Oberfläche der zweiten Schicht ist somit abdeckungsfrei ausgebildet. Sie steht damit in unmittelbarem Kontakt zu korrosiven und Verschleiß verursachenden Medien. Es hat sich herausgestellt, dass die Unter-, Zwischen- oder Überordnung weiterer Schichten sowohl für die Korrosions- als auch die Verschleißeigenschaften schädlich sind. Daher ist die Beschichtung eine mit einem lediglich zweischichtigen Schichtsystem. Gemäß der Erfindung enthält die Beschichtung Partikel, welche ausschließlich in der zweiten Schicht enthalten sind. Die Partikel sind vorzugsweise aus einem Material gebildet, welches eine vergleichsweise hohe Härte aufweist. Hierdurch kann vorteilhafterweise die Verschleißfestigkeit und das Ritzverhalten der erfindungsgemäßen Beschichtung weiter verbessert werden. Erfindungsgemäß sind die Partikel aus Bor oder Borverbindungen, ausgewählt aus Borcarbid oder Bornitrid. Einsetzbar aber nicht erfindungsgemäß sind Partikel aus Siliciumverbindungen oder Titanverbindungen. Es hat sich gezeigt, dass insbesondere die Carbide und Nitride der vorgenannten Elemente besonders vorteilhafte Eigenschaften hinsichtlich Verschleißfestigkeit und Ritzverhalten aufweisen. Einsetzbare Siliciumverbindungen sind demnach Siliciumcarbid (SiC) und/oder Siliciumnitrid (Si3N4). Einsetzbare Titanverbindungen sind Titannitrid (TiN), Titancarbonitrid (Ti(C, N)) und/oder Titanaluminiumnitrid (TiAIN). Erfindungsgemäße Borverbindungen sind Borcarbid (B4C) und/oder Bornitrid, insbesondere -Bornitrid (CBN; kubisches kristallines Bornitrid). Im Allgemeinen führen alle vorgenannten Verbindungen alleine oder in Kombination miteinander zu einer Verbesserung der Verschleißfestigkeit und des Ritzverhalten der hierin offenbarten Beschichtung. Besonders vorteilhaft hat sich hierbei die Verwendung von Borcarbid erwiesen. Erfindungsgemäß sind die Partikel lediglich in der zweiten Schicht enthalten. Es hat sich diesbezüglich gezeigt, dass hierdurch eine vergleichsweise große Steigerung der Schutzeigenschaften mit minimalem Materialeinsatz erreicht werden kann. Vorteilhafterweise ist hierdurch ein optimierter Kompromiss zwischen Korrosions-Verschleißschutz und Ritzverhalten und Herstellungsaufwand und Herstellungskosten gelungen.According to a feature not according to the invention, the second layer of at least tin, nickel and antimony contains at least one further alloying component. This is for example a metal from the group copper, iron, tungsten or cobalt. It has been found that the corrosion resistance and the wear resistance can be further improved by the aforementioned components. According to the applicant's current state of knowledge, the synergetic interaction of these components with antimony results in an increase in the electrochemical stabilization of the individual layers of the coating according to the invention. The first layer is deposited directly, ie without any intermediate layers on the substrate. The second layer is deposited directly, ie without any intermediate layers on the first layer. The surface of the second layer facing away from the first layer carries no further layers. Said surface of the second layer is thus formed free of cover. She is in direct contact with it corrosive and wear-causing media. It has been found that the under, intermediate or superposition of further layers are detrimental to both the corrosion and wear properties. Therefore, the coating is one with a two-layered layer system only. According to the invention, the coating contains particles which are contained exclusively in the second layer. The particles are preferably formed from a material which has a comparatively high hardness. In this way, advantageously, the wear resistance and the scratch behavior of the coating according to the invention can be further improved. According to the invention, the particles are boron or boron compounds selected from boron carbide or boron nitride. Applicable but not according to the invention are particles of silicon compounds or titanium compounds. It has been found that, in particular, the carbides and nitrides of the abovementioned elements have particularly advantageous properties with regard to wear resistance and scratch behavior. Applicable silicon compounds are therefore silicon carbide (SiC) and / or silicon nitride (Si 3 N 4 ). Usable titanium compounds are titanium nitride (TiN), titanium carbonitride (Ti (C, N)) and / or titanium aluminum nitride (TiAIN). Boron compounds according to the invention are boron carbide (B 4 C) and / or boron nitride, in particular boron nitride (CBN; cubic crystalline boron nitride). In general, all of the above compounds, alone or in combination, improve the wear resistance and scratch performance of the coating disclosed herein. Particularly advantageous in this case has proven the use of boron carbide. According to the invention, the particles are contained only in the second layer. It has been shown that in this way a comparatively large increase in the protection properties can be achieved with minimal use of materials. Advantageously, this is an optimized compromise between corrosion wear protection and scribe behavior and manufacturing and manufacturing costs succeeded.
Die Beschichtung kann dem Grunde nach auf jedem beliebigen Substrat aufgebracht werden. Insbesondere auf Polymersubstraten und Metallsubstraten. Metallsubstrate, insbesondere nichtrostende Edelstähle, sind als Hauptsubstrat im Bereich der Bauteile, die Seewasser ausgesetzt sind besonderes bevorzugte Substrate und werden durch die erfindungsgemäße Beschichtung besonders gut vor Korrosion und Verschleiß geschützt.The coating can basically be applied to any substrate. In particular on polymer substrates and metal substrates. Metal substrates, in particular stainless stainless steels, are particularly preferred substrates as the main substrate in the region of the components which are exposed to seawater and are protected particularly well against corrosion and wear by the coating according to the invention.
Hinsichtlich des Verfahrens wird die Aufgabe der Erfindung durch ein Verfahren zur Beschichtung einer Substratoberfläche zum Zwecke des Korrosions- und Abriebschutzes gemäß Anspruch 3 gelöst. With regard to the method, the object of the invention is achieved by a method for coating a substrate surface for the purpose of corrosion and abrasion protection according to
In einer bevorzugten Ausführungsform der Erfindung wird die Beschichtung mit einer Gesamtschichtdicke von 2 bis 150 µm auf dem Substrat abgeschieden, vorzugsweise mit 10 bis 100 µm, weiter bevorzugt mit 50 bis 75 µm. Insbesondere im Bereich von hochseetauglichen Großbauteilen die einer vergleichsweise großen mechanischen Belastung ausgesetzt sind, wie insbesondere bei der Offshore-Gewinnung von Erdöl, Erdgas oder Windkraft oder auch bei der Hochseeschifffahrt, werden besonders bevorzugt Gesamtschichtdicken von 100 bis 150 µm auf dem Substrat abgeschieden. Gemäß einem weiteren bevorzugten Merkmal der Erfindung wird die zweite Legierungsschicht aus wenigstens Zinn, Nickel und Antimon mit einer Schichtdicke von wenigstens 1 µm, vorzugsweise von wenigstens 5 µm und noch bevorzugter von wenigstens 10 µm auf der ersten Schicht abgeschieden. Bei Bauteilen, die besonderer mechanischer Belastung ausgesetzt sind, kann die Schichtdicke beispielsweise auch mit 20 µm, 30 µm, 40 µm, 75 µm, 100 µm oder noch dicker abgeschieden werden.In a preferred embodiment of the invention, the coating is deposited on the substrate with a total layer thickness of 2 to 150 .mu.m, preferably with 10 to 100 .mu.m, more preferably with 50 to 75 .mu.m. Particularly in the field of large-scale suitable large components which are exposed to a comparatively large mechanical load, in particular in the offshore extraction of oil, natural gas or wind power or in ocean shipping, particularly preferably total layer thicknesses of 100 to 150 microns are deposited on the substrate. According to a further preferred feature of the invention, the second alloy layer of at least tin, nickel and antimony having a layer thickness of at least 1 μm, preferably of at least 5 μm and more preferably of at least 10 μm, is deposited on the first layer. In the case of components which are exposed to particular mechanical stress, the layer thickness can also be deposited, for example, at 20 μm, 30 μm, 40 μm, 75 μm, 100 μm or even thicker.
Erfindungsgemäß wird als erste Schicht eine Bronze-Legierungsschicht abgeschieden. Gemäß der Erfindung wird die erste Schicht hierbei als eine binäre Kupfer-Zinn-Bronze abgeschieden. Sowohl Knetlegierungen als auch Gusslegierungen können dem Grunde nach als erste Schicht der erfindungsgemäßen Beschichtung abgeschieden werden. Bevorzugt werden jedoch Gusslegierungen mit einem Zinnanteil von wenigstens 9 Gew.-%, besonders bevorzugt sind 9 bis 13 Gew.-% und weiter bevorzugt 11 Gew.-% abgeschieden. Neben den klassischen Bronzen können darüber hinaus auch andere, gemeinhin als Bronzen bezeichnete Kupferlegierungen, wie insbesondere Aluminiumbronzen, Berylliumbronzen oder Bleibronzen die unter den Oberbegriff der Bronze fallen als erste Schicht abgeschieden werden. Aufgrund ihrer exzellenten Seewasserbeständigkeit ist es bevorzugt, Aluminiumbronze als erste Schicht abzuscheiden.According to the invention, a bronze alloy layer is deposited as the first layer. According to the invention, the first layer is deposited here as a binary copper-tin bronze. Both wrought alloys and cast alloys can basically be deposited as the first layer of the coating according to the invention. However, casting alloys with a tin content of at least 9% by weight, particularly preferably 9 to 13% by weight and more preferably 11% by weight, are preferably deposited. In addition to the classic bronzes, other copper alloys, commonly referred to as bronzes, such as, in particular, aluminum bronzes, beryllium bronzes or lead bronzes, which fall under the generic term of bronze, can also be deposited as the first layer. Because of its excellent sea water resistance, it is preferred to deposit aluminum bronze as the first layer.
Gemäß einem nicht erfindungsgemäßen Merkmal wird zur Bildung der zweiten Schicht neben den erfindungsgemäßen Komponenten Zinn, Nickel und Antimon wenigstens eine weitere Legierungskomponente abgeschieden. Hierzu wird beispielsweise ein Metall aus der Gruppe Kupfer, Eisen, Wolfram oder Kobalt verwendet. Es hat sich gezeigt, dass die Korrosionsbeständigkeit und die Verschleißfestigkeit durch vorgenannte Komponenten weiter verbessert werden kann.According to a feature not according to the invention, in addition to the components tin, nickel and antimony according to the invention, at least one further alloying component is deposited to form the second layer. For this purpose, for example, a metal from the group copper, iron, tungsten or cobalt is used. It has been shown that the Corrosion resistance and wear resistance can be further improved by the aforementioned components.
Gemäß der Erfindung werden Partikel in die erfindungsgemäße Beschichtung eingebracht, nämlich ausschließlich in die zweite Schicht. Die Partikel sind vorzugsweise aus einem Material gebildet, welches eine vergleichsweise hohe Härte aufweist. Hierdurch kann vorteilhafterweise die Verschleißfestigkeit und das Ritzverhalten der erfindungsgemäßen Beschichtung weiter verbessert werden. Erfindungsgemäß sind Partikel aus Bor oder aus Borverbindungen, ausgewählt aus Borcarbid oder Bornitrid. Einsetzbar aber nicht erfindungsgemäß sind Partikel aus Siliciumverbindungen oder Titanverbindungen. Es hat sich gezeigt, dass insbesondere die Carbide und Nitride der vorgenannten Elemente besonders vorteilhafte Eigenschaften hinsichtlich Verschleißfestigkeit aufweisen. Einsetzbare Siliciumverbindungen sind demnach Siliciumcarbid (SiC) und/oder Siliciumnitrid (Si3N4). Einsetzbare Titanverbindungen sind Titannitrid (TiN), Titancarbonitrid (Ti(C, N)) und/oder Titanaluminiumnitrid (TiAIN). Erfindungsgemäße Borverbindungen sind Borcarbid (B4C) und/oder Bornitrid, insbesondere -Bornitrid (CBN; kubisches kristallines Bornitrid). Im Allgemeinen können alle vorgenannten Verbindungen alleine oder in Kombination miteinander in die Beschichtung eingebracht werden. Als besonders vorteilhaft hat sich hierbei allerdings die ausschließliche Verwendung von Borcarbiden erwiesen. Gemäß der Erfindung werden die Partikel lediglich in die zweite Schicht eingebracht, wodurch ein optimierter Kompromiss zwischen Korrosions- und Verschleißschutz auf der einen Seite und Herstellungsaufwand und Herstellungskosten auf der anderen Seite erreicht werden kann.According to the invention, particles are introduced into the coating according to the invention, namely exclusively into the second layer. The particles are preferably formed from a material which has a comparatively high hardness. In this way, advantageously, the wear resistance and the scratch behavior of the coating according to the invention can be further improved. According to the invention, particles are boron or boron compounds selected from boron carbide or boron nitride. Applicable but not according to the invention are particles of silicon compounds or titanium compounds. It has been shown that in particular the carbides and nitrides of the aforementioned elements have particularly advantageous properties in terms of wear resistance. Applicable silicon compounds are therefore silicon carbide (SiC) and / or silicon nitride (Si 3 N 4 ). Usable titanium compounds are titanium nitride (TiN), titanium carbonitride (Ti (C, N)) and / or titanium aluminum nitride (TiAIN). Boron compounds according to the invention are boron carbide (B 4 C) and / or boron nitride, in particular boron nitride (CBN; cubic crystalline boron nitride). In general, all the above-mentioned compounds may be incorporated in the coating alone or in combination with each other. However, the exclusive use of boron carbides has proven to be particularly advantageous. According to the invention, the particles are introduced only in the second layer, whereby an optimized compromise between corrosion and wear protection on the one hand and manufacturing costs and manufacturing costs on the other hand can be achieved.
Die Abscheidung der einzelnen Schichten der Beschichtung kann in Abhängigkeit der Art der Schicht in der im Stand der Technik üblichen außenstromlosen oder elektrolytischen Weise erfolgen. So wird beispielsweise bei der Abscheidung der Bronzeschicht als erste Schicht eine elektrolytische Abscheidung unter Anlegung einer geeigneten Abscheidespannung zwischen der Substratoberfläche und einer Gegenelektrode und Verwendung eines üblichen Bronzeelektrolyten (wässriger, kupfer- und zinnhaltiger Elektrolyt) bevorzugt.The deposition of the individual layers of the coating can be carried out in the state-of-the-art electroless or electrolytic manner, depending on the type of layer. Thus, for example, in the deposition of the bronze layer as the first layer, an electrolytic deposition under application of a suitable deposition voltage between the substrate surface and a counter electrode and using a conventional bronze electrolyte (aqueous, copper and tin-containing electrolyte) is preferred.
Die Abscheidung der erfindungsgemäß vorzusehenden Zinn-Nickel-Antimon-Legierungsschicht als zweite Schicht kann ebenfalls elektrolytisch unter Anlegung einer Abscheidespannung zwischen der Substratoberfläche und einer geeigneten Gegenelektrode oder autokatalytisch unter Verwendung geeigneter Reduktionsmittel erfolgen.The deposition of the present invention tin-nickel-antimony alloy layer as a second layer can also be electrolytically under application of a Separation voltage between the substrate surface and a suitable counter electrode or carried out autocatalytically using suitable reducing agents.
Die Abscheidung der Partikel erfolgt erfindungsgemäß in einem Dispersionsbad. Sollen nicht erfindungsgemäß in die gesamte Beschichtung Partikel eingebracht werden, so ist die Abscheidung sowohl der ersten als auch der zweiten Schicht in einem Dispersionsbad durchzuführen. Sollen die Partikel lediglich in eine der beiden Schichten, wie erfindungsgemäß ausschließlich in die zweite Schicht, eingebracht werden, so muss lediglich die Abscheidung der entsprechenden Schicht, in welche die Partikel eingebracht werden sollen, in einem Dispersionsbad erfolgen. Zur Ausbildung einer homogenen Verteilung der Partikel in der Beschichtung ist es bevorzugt vorgesehen, die Partikel während des Abscheidevorgangs der jeweiligen Schicht homogen im Dispersionsbad zu verteilen. Hierfür kann bevorzugt die Einbringung eines Gases zur Umwälzung des Elektrolyten vorgesehen sein. Das Gas wird bevorzugt vom Boden des Dispersionsbades her in Form feiner Bläschen in das Dispersionsbad eingebracht. Die Bläschen haben bevorzugter Weise einen Durchmesser im Bereich 0,5-10 µm, bevorzugt 0,5-5 µm. Weiter bevorzugt wird das Gas entweder über Düsen am Boden des Dispersionsbades in dieses eingebracht. Alternativ hierzu wird das Gas direkt durch eine gasdurchlässige und flüssigkeitsdichte Membran, die den Boden des Bades bildet eingeleitet. Als Gas wird vorzugsweise ein Schutzgas verwendet. Dies stellt sicher, dass keine unerwünschten Nebenreaktionen des Gases mit den Legierungsbestandteilen stattfinden. Als Schutzgas werden insbesondere im Stand der Technik bekannte Schutzgase wie Stickstoff oder Argon verwendet.The deposition of the particles takes place according to the invention in a dispersion bath. If particles are not to be introduced into the entire coating according to the invention, the deposition of both the first and the second layer is to be carried out in a dispersion bath. If the particles are to be introduced only into one of the two layers, as in the invention exclusively into the second layer, then only the deposition of the corresponding layer into which the particles are to be introduced must take place in a dispersion bath. To form a homogeneous distribution of the particles in the coating, it is preferably provided to distribute the particles homogeneously in the dispersion bath during the deposition process of the respective layer. For this purpose, the introduction of a gas for circulating the electrolyte may preferably be provided. The gas is preferably introduced into the dispersion bath from the bottom of the dispersion bath in the form of fine bubbles. The bubbles preferably have a diameter in the range 0.5-10 μm, preferably 0.5-5 μm. More preferably, the gas is introduced either via nozzles at the bottom of the dispersion bath in this. Alternatively, the gas is introduced directly through a gas-permeable and liquid-tight membrane which forms the bottom of the bath. The gas used is preferably a protective gas. This ensures that there are no unwanted side reactions of the gas with the alloying constituents. Protective gas used in particular in the prior art known protective gases such as nitrogen or argon.
Alternativ oder in Kombination zur Gaseinleitung kann eine homogene Verteilung der Partikel im Dispersionsbad auch über Elektrolytbewegung erreicht werden. Vorzugsweise können hierfür Rühranlagen für eine intern induzierte Elektrolybewegung im Dispersionsbad verwendet werden. Alternativ oder in Kombination mit der intern induzierten Elektrolybewegung, kann der Elektrolyt auch durch externe Anregung in Bewegung versetzt werden. Dies wird vorzugsweise durch eine hierfür geeignete Bewegung des Behälters des Dispersionsbades erreicht.Alternatively or in combination with the gas introduction, a homogeneous distribution of the particles in the dispersion bath can also be achieved via electrolyte movement. For this purpose, stirring devices for an internally induced movement of electrolytes in the dispersion bath can preferably be used for this purpose. Alternatively or in combination with the internally induced movement of electrolytes, the electrolyte can also be set in motion by external excitation. This is preferably achieved by a suitable movement of the container of the dispersion bath.
Die erfindungsgemäß abgeschiedenen Schichtsysteme eignen sich insbesondere zur Beschichtung von Bauteilen im Bereich der Hydrauliktechnik, wie beispielsweise Kolbenstangen, Kolbenrohre, Speicherstangen, Hubzylinder, Wippzylinder etc., für die Beschichtung von Druckwalzen im Bereich der Druckmaschinentechnik, für die Beschichtung von Anlagenbauteilen und -komponenten im Bereich der Marinekonstruktionstechnik, insbesondere im Bereich des Schiffbaus sowie der Offshore-Gewinnung von Windkraft, Erdgas und Erdöl, sowie im Bereich des Motorenbaus.The layer systems deposited according to the invention are particularly suitable for coating components in the field of hydraulic engineering, such as piston rods, piston tubes, storage rods, lifting cylinders, luffing cylinders, etc., for the Coating of printing rolls in the field of printing technology, for the coating of plant components and components in the field of marine engineering, in particular in the field of shipbuilding and the offshore extraction of wind power, natural gas and crude oil, as well as in the field of engine construction.
Alle Merkmale der erfindungsgemäßen Beschichtung dienen der synergetischen Verbesserung der Korrosionsbeständigkeit und der Verschleißfestigkeit. Die Vorteile der Erfindung werden hierbei erreicht, ohne umweltschädliche Chrom-haltige Legierungen zu verwenden.All features of the coating according to the invention serve the synergetic improvement of corrosion resistance and wear resistance. The advantages of the invention are achieved here, without using environmentally harmful chromium-containing alloys.
Die Erfindung wird nachfolgend anhand eines für den Fachmann nicht beschränkend zu verstehenden Ausführungsbeispiels näher erläutert. Dabei zeigt
- Fig.1
- die erfindungsgemäße Beschichtung eines Substrates mit einer erfindungsgemäßen Beschichtung in schematischer Ansicht.
- Fig.1
- the coating of a substrate according to the invention with a coating according to the invention in a schematic view.
In
Alsdann erfolgt die Abscheidung einer binären Kupfer-Zinn-Bronzeschicht als erste Schicht unmittelbar auf der Substratoberfläche. Vorliegend wird die Bronzeschicht mit einem Zinnanteil von 11 Gew.-% abgeschieden. Nach vollendeter Abscheidung liegt die Schichtdicke der Bronzeschicht im Mittel bei 45 µm. Anschließend wird das mit der ersten Schicht beschichtete Substrat aus dem galvanischen Bronzebad entnommen, Elektrolytreste entfernt und in ein galvanisches Dispersionsbad eingebracht. Das Dispersionsbad enthält einen wässrigen Elektrolyten 3 mit einer Nickelquelle, einer Zinnquelle und einer Antimonquelle. Zur bestimmungsgemäßen unmittelbaren Abscheidung der zweiten Schicht auf der bronzeschichtseitigen Oberfläche der Bronzeschicht wird zwischen besagter Oberfläche und einer geeigneten Gegenelektrode eine Abscheidespannung angelegt.Then, the deposition of a binary copper-tin-bronze layer as a first layer takes place directly on the substrate surface. In the present case, the bronze layer is deposited with a tin content of 11 wt .-%. After completion of the deposition, the layer thickness of the bronze layer is on average at 45 microns. Subsequently, the substrate coated with the first layer is removed from the galvanic bronze bath, electrolyte residues are removed and introduced into a galvanic dispersion bath. The dispersion bath contains an
Ferner enthält das Dispersionsbad Borcarbidpartikel 4. Diese werden zur bestimmungsgemäßen Einbringung in die zweite Schicht homogen im Dispersionsbad verteilt. Hierzu wird der Behälter des Dispersionsbades kontinuierlich bewegt. Nach vollendeter Abscheidung liegt die Schichtdicke der zweiten Legierungsschicht im Mittel bei 45 m. In die zweite Schicht eingebracht sind die Borcarbidpartikel 4. Die Einbringung der Partikel in die zweite Schicht unterliegt einem Gleichgewicht. Es ist daher erforderlich, die Partikel dem Dispersionsbad in einem auf die einzubringende Menge bezogenen Überschuss zuzugeben. Hierdurch wird sowohl die Einbringung der Partikel in die zweite Schicht beschleunigt und die absolute Menge der eingebrachten Partikel erhöht. Dies führt in der Konsequenz vorteilhafterweise zu einer Verbesserung der Korrosions- und Verschleißeigenschaften der erfindungsgemäßen Beschichtung.Furthermore, the dispersion bath contains
- 11
- Substratsubstratum
- 22
- Elektrolyt zur Abscheidung der ersten SchichtElectrolyte for the deposition of the first layer
- 33
- Elektrolyt zur Abscheidung der zweiten SchichtElectrolyte for the deposition of the second layer
- 44
- Borcarbidpartikelboron carbide
Claims (4)
- A layer system comprising a substrate and a coating of the substrate surface for corrosion and wear protection, the coating consisting of a first layer deposited on the substrate surface and a second layer deposited on the first layer, wherein the first layer is a bronze alloy layer which is composed of a binary copper-tin bronze,
characterized in that
the second layer is an alloy layer which is composed of tin, nickel, antimony and particles of boron or a boron compound selected from boron carbide or boron nitride, and that the first layer is free from these particles. - A layer system according to claim 1, characterized in that the first layer contains at least 9 % by weight tin.
- A method for coating a substrate surface for corrosion and wear protection, in which a first layer will be deposited on the substrate surface and in which a second layer will be deposited on the first layer, wherein a bronze alloy layer composed of a binary copper-tin bronze will be deposited as first layer, characterized in that an alloy layer composed of tin, nickel, antimony and particles of boron or a boron compound selected from boron carbide or boron nitride will be deposited as second layer, wherein the deposition of the second layer will be carried out in a dispersion bath comprising particles of boron or the boron compound, wherein the particles will be exclusively introduced into the second layer.
- A use of a layer system according to one of the claims 1 or 2 for providing structural parts and/or hydraulic components that are exposed to sea water with corrosion and abrasion resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15157442.3A EP3064613B1 (en) | 2015-03-03 | 2015-03-03 | Layered coating system having improved corrosion and wear resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15157442.3A EP3064613B1 (en) | 2015-03-03 | 2015-03-03 | Layered coating system having improved corrosion and wear resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3064613A1 EP3064613A1 (en) | 2016-09-07 |
| EP3064613B1 true EP3064613B1 (en) | 2018-08-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15157442.3A Not-in-force EP3064613B1 (en) | 2015-03-03 | 2015-03-03 | Layered coating system having improved corrosion and wear resistance |
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| DE102017005221A1 (en) * | 2017-05-31 | 2018-12-06 | Hochschule Mittweida (Fh) | Hard and wear-resistant dispersion layer with a metallic matrix on substrates |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941903A (en) * | 1972-11-17 | 1976-03-02 | Union Carbide Corporation | Wear-resistant bearing material and a process for making it |
| DE3621184A1 (en) * | 1986-06-25 | 1988-01-07 | Glyco Metall Werke | LAYERING MATERIAL AND METHOD FOR ITS PRODUCTION BY VACUUM PLASMA SPRAYING |
| DE4443461C1 (en) * | 1994-12-07 | 1996-07-04 | Wieland Werke Ag | Copper@ (alloy) composite strip or wire material used in electromechanical or electrooptical applications |
| EP2233611A1 (en) * | 2009-03-24 | 2010-09-29 | MTV Metallveredlung GmbH & Co. KG | Layer system with improved corrosion resistance |
| AT509111B1 (en) * | 2009-12-10 | 2011-09-15 | Miba Gleitlager Gmbh | SLIDING LAYER |
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2015
- 2015-03-03 EP EP15157442.3A patent/EP3064613B1/en not_active Not-in-force
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|---|---|
| EP3064613A1 (en) | 2016-09-07 |
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