EP3484632A1 - Substrat mit korrosionsschutzsystem - Google Patents
Substrat mit korrosionsschutzsystemInfo
- Publication number
- EP3484632A1 EP3484632A1 EP17740650.1A EP17740650A EP3484632A1 EP 3484632 A1 EP3484632 A1 EP 3484632A1 EP 17740650 A EP17740650 A EP 17740650A EP 3484632 A1 EP3484632 A1 EP 3484632A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substrate
- corrosion protection
- corrosion
- protection system
- modulus
- 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.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 132
- 239000000758 substrate Substances 0.000 title claims abstract description 86
- 230000007797 corrosion Effects 0.000 claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 229910001220 stainless steel Inorganic materials 0.000 claims description 29
- 238000013532 laser treatment Methods 0.000 claims description 27
- 229910052804 chromium Inorganic materials 0.000 claims description 23
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010935 stainless steel Substances 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 238000010894 electron beam technology Methods 0.000 claims description 10
- 230000006870 function Effects 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000013535 sea water Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004887 air purification Methods 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000013047 polymeric layer Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 70
- 239000000523 sample Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- 239000011651 chromium Substances 0.000 description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 21
- 238000005259 measurement Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 17
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 15
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 238000007373 indentation Methods 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 230000005284 excitation Effects 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 238000000313 electron-beam-induced deposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000003821 2-(trimethylsilyl)ethoxymethyl group Chemical group [H]C([H])([H])[Si](C([H])([H])[H])(C([H])([H])[H])C([H])([H])C(OC([H])([H])[*])([H])[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
- B05D2202/15—Stainless steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/30—Change of the surface
Definitions
- the invention relates to a substrate with corrosion protection system, wherein the corrosion protection system is arranged on the surface of the substrate and a plasma polymer layer with certain lower limits of the modulus and certain maxima of the Si 2p peaks and between the substrate and the plasma polymer layer a zone with respect to the Substrate enriched corrosion protection elements comprises.
- the invention further relates to the use of the above-described corrosion protection system for achieving a corrosion protection and to a method for producing a substrate with a corrosion protection system.
- Corrosion protection is an important technical task, because corrosion destroys assets and ensures machine downtime in production processes. Therefore, the most different methods exist to equip surfaces to prevent corrosion. These include primarily passive corrosion protection processes by painting or the application of galvanic processes. For example, surfaces are anodized, galvanized, burnished, chromated or phosphated. In many cases one tries, for example to reinforce the passivating surface of stainless steels through the use of wet-chemical processes (electrochemical processes). In addition to passive corrosion protection processes, there are also some active processes involving e.g. Coatings in the event of a defect corrosion-inhibiting substances can deliver.
- the corrosion protection layer Due to special requirements of the corrosion protection layer, such as a good heat transfer in heat exchangers (colloquially heat exchanger called) or high precision in the imaging of the surface structure to be protected (edges, embossing, etc.), there is a need for thin-film corrosion protection layers ( ⁇ 10 ⁇ and in particular ⁇ 2.5 ⁇ ), which change the surface to be protected as little as possible, allow a good thermal heat transfer, do not give off heavy metals and do not excessively burden the entire substrate with heat ( ⁇ 100 ° C) during coating in order not to promote diffusion processes.
- This need can be covered, for example, with plasma-polymeric anticorrosive coatings, which are typically applied in a layer thickness range of 10 to 5000 nm, preferably by means of a cold process.
- the plasma-polymeric coating method is basically suitable for penetrating into narrow structures, such as are frequently the case with a heat exchanger, or also for achieving the accuracy of fit of the component.
- stainless steels Due to their microstructure, stainless steels are initially divided into 4 different groups: austenite, ferrites, duplex and martensite. Stainless steels contain 12 to 26% by weight of chromium and 6 to 25% by weight of nickel [L. Wegrelius]. Other elements may be added to the steel to modify its properties.
- chromium and molybdenum increases the corrosion resistance.
- the quantity stated above is sufficient to produce a protective layer (passivation) under the influence of air and moisture.
- increasing chromium and molybdenum content increases the corrosion resistance.
- JP 01242787 describes how stainless steel or Inconel is laser processed to form a corrosion resistant oxide layer.
- JP 08104949 aims in a similar direction but focuses on austenitic steels.
- RU 2287414 and KR 964574 utilize the effect of laser treatment to achieve a color design of the steels or other metallic materials by oxide formation.
- the latter application also makes use of the possibility of applying acrylic material or polycarbonate before the laser treatment in order to produce a transparent protective layer.
- CN 10491 1329 uses laser treatment of stainless steel to create a superhydrophobic corrosion resistant surface.
- the surface is processed in such a way that a corresponding microstructure is created in the metal surface.
- the temperature input can be so great that the entire material or only individual alloy constituents, depending on the ablation threshold, are directly sublimated and thereby eliminated. will wear.
- the diffusion of special elements of the alloy to the surface can be excited.
- the laser interaction depth is typically in the range of a few to a few ⁇ .
- E modulus [GPa] x> 0.5 and ⁇ 2.0, preferably x> 0.5 and ⁇ 1.8
- a "zone of enriched corrosion protection elements" is either a layer with distinct layer boundaries to the substrate or the area in which there is a gradient with an increasing concentration of corrosion protection elements, based on the concentration of corrosion protection elements in the substrate is not a plasma polymer layer and particularly preferably produced or producible by a modification of the substrate material, most preferably without the addition of further material.
- Corrosion protection elements in the context of the present text are chromium, manganese, molybdenum, silicon and titanium, with preferred corrosion protection elements being chromium, molybdenum and manganese.
- enriched relative to the substrate means that the sum of the anticorrosive elements is enriched in the substrate relative to the sum of the anticorrosive elements (in each case amount of substance), preferably by at least> 2 at%, more preferably> 5 at%, based on the sum of
- the determination of the corrosion protection elements enriched in the substrate or in the zone with corrosion protection elements enriched with respect to the substrate is carried out by means of EDX, as described in measuring example 3, in the substrate or the sum of the elements contained in the transition zone.
- Plasma polymers differ from classical polymers in that their preparation is fragmented by usually gaseous precursors. Accordingly, unlike classical polymers, plasma polymers do not show regular repetitive subunits, even if - depending on the manufacturing process - a close arrangement can not be ruled out.
- the modulus of elasticity of the coating in the sense of the present invention is determined by means of the method described in measurement example 1.
- the C / O ratio is determined by XPS (x-ray photoelectron spectroscopy) in case of doubt according to the measurement example 2. The same applies to the shift of the maximum of the Si 2p peak.
- the plasma polymer layer is already known as a corrosion protection layer, but exhibits inadequate adhesion especially when used on steel.
- E 0.75 - 12.4, preferably 1, 0 - 12.4, more preferably 1, 25 - 12.4 and / or the surface energy of the surface of the plasma polymer layer is determined in terms of their upper limit by the following function (3) :
- the surface energy of the surface of the plasma polymer layer with respect to its lower limit is preferably determined by the following function (4):
- the surface energy and the polar component of the surface energy is determined in case of doubt according to measurement example 3.
- a preferred substrate according to the invention with a corrosion protection system is one in which the zone with corrosion protection elements enriched with respect to the substrate has an enrichment gradient of the corrosion protection elements which increases away from the substrate.
- Such a substrate or the corresponding zone with corrosion protection elements enriched with respect to the substrate is accessible on the one hand via a number of enrichment processes preferably to be used inter alia (see also below), and on the other hand it makes possible, in a particular degree, an improvement in the adhesion of the plasma polymer layer to be used according to the invention.
- a substrate according to the invention with a corrosion protection system, the zone being produced or producible with corrosion protection elements enriched by means of a laser treatment, by means of vacuum-assisted vapor deposition, by sputtering, by thermal spraying, by electron beam treatment, by electrochemical deposition and by vapor deposition.
- Particularly preferred are processes in which no material is added for producing the enrichment of the anti-corrosion elements.
- the zone with corrosion protection elements enriched with respect to the substrate was produced by means of a laser treatment.
- the adhesion behavior of the plasma polymer layer to be used could be markedly improved, in particular by the laser surface modification.
- the inventors were able to observe, without being bound by this theory, that in particular in steel surfaces by the preferred method for generating a zone enriched with respect to the substrate anti-corrosion elements, especially by laser treatment, the iron content in iron-containing substrates such as steel or stainless steel is significantly reduced so that in the case of, for example, chromium-containing steel, a chromium-enriched oxide on the surface remains.
- chromium-containing steel a chromium-enriched oxide on the surface remains.
- the laser-treated surface can have an interference-related color appearance, which depends on the layer thickness of this area, the layer composition and the actual substrate material.
- the additional application of the plasma polymer coating can lead to a further change in the interference color.
- the laser treatment according to Example 1 given below leads to an interference color with a golden to golden-brown hue.
- a pulsed laser with a pulse duration in the ns range and an energy density on the substrate surface of at least 100 mJ / cm 2 .
- a laser having a wavelength in the near and middle IR range is used, particularly preferably with a wavelength of 1064 nm.
- An improvement of the corrosion protection in the context of the present invention is at least present if, due to the action of strong acids, a surface change which is slower than the uncoated state, eg due to the formation of corrosion products typical of the alloy, is present. It is preferable to test as a quick test the coated surface with 25% HCl at 35 ° C over a period of 15 to 60 minutes and compare it with an uncoated surface of the same type of material which has been subjected to the same load. An improvement The surface resistance to acids or alkalis is improved if the described test shows a surface change which is slowed down by the coating according to the invention, preferably already visibly with the naked eye.
- a substrate according to the invention with a corrosion protection system may be preferred, wherein the zone with corrosion protection elements enriched with respect to the substrate is a layer delimited from the substrate.
- the zone according to the invention to be provided with anticorrosive elements enriched with respect to the substrate is an independent layer which can be applied by means of a suitable coating method, preferably with one of the abovementioned.
- CVD and PVD methods can be used to apply the zone with corrosion protection elements enriched in relation to the substrate, from which the skilled person will select the suitable ones.
- a substrate according to the invention with a corrosion protection system, the zone having anti-corrosion elements enriched with respect to the substrate comprising> 12 atomic%, preferably> 15 atomic%, particularly preferably> 20 atomic% corrosion protection elements, measured by XPS.
- XPS atomic fraction
- a substrate according to the invention having a corrosion protection system, the substrate consisting of> 50 at% of iron, preferably of steel and more preferably of stainless steel, preferably measured by means of EDX (Measuring Example 3)
- Steel in the sense of the present text is a metallic alloy which consists primarily of iron. According to DIN EN 10020: 2000-07, the iron alloy contains a carbon content of ⁇ 2.06% (A limited number of chromium steels may also have a higher carbon content).
- Stainless steel in the sense of the present text is according to EN 10020 a steel with a special degree of purity, eg with a low sulfur and phosphorus content.
- alloyed stainless steels in particular chromium, chromium nickel, chromium molybdenum and titanium steel.
- chromium, chromium nickel, chromium molybdenum and titanium steel As an example of such noble
- the materials X5CrNi18-10, X5CrNiMo17-12-2 and X2CrNiMo17-12-2 are mentioned.
- a substrate according to the invention with a corrosion protection system selected from the group consisting of heat exchanger, heat exchanger, medical device or tool, fitting for e.g. Furniture, vehicles or trailers, pullout unit e.g. for ovens, kitchens or furniture; Decorative and functional elements for means of transport, e.g. Moldings, railings, components for (sea) water desalination or filtration plants and chemical exhaust air purification, such as e.g. Housing or piping, components for flue gas systems and seawater use.
- a corrosion protection system selected from the group consisting of heat exchanger, heat exchanger, medical device or tool, fitting for e.g. Furniture, vehicles or trailers, pullout unit e.g. for ovens, kitchens or furniture; Decorative and functional elements for means of transport, e.g. Moldings, railings, components for (sea) water desalination or filtration plants and chemical exhaust air purification, such as e.g. Housing or piping, components for flue gas
- Part of the invention is also the use of a corrosion protection system as defined above for achieving a corrosion protection on a substrate described above, wherein the substrate is> 50 at% of iron, preferably of steel and more preferably of stainless steel and more preferably represents one of the substrate types, which are explicitly described above.
- Part of the invention is also a method for producing a substrate according to the invention with corrosion protection system, comprising the steps: a) providing a substrate, preferably as described above as preferred, b) generating a zone enriched with respect to the substrate corrosion protection elements, preferably as above preferred and c) depositing a plasma polymer layer as defined above.
- step b) one of the preferred treatment variants is used, especially that a laser treatment is included or that the step b) consists of a laser treatment.
- the nanoindentation is a test technique, with a fine diamond tip (three-sided pyramid [Berkovich], radius few 100nm) the hardness of surface coating can be determined.
- a fine diamond tip three-sided pyramid [Berkovich], radius few 100nm
- the hardness of surface coating can be determined.
- it does not measure the remaining indentation cavity impressed by a normal force, but assumes a penetration depth-dependent cross-sectional area of the nanoindenter. This depth-dependent cross-sectional area is determined using a reference sample of known hardness (usually fused silica).
- nanoindentation uses a sensitive deflection sensor (capacitive plates) with which the penetration depth can be precisely measured with increasing and decreasing normal force - unlike the classical procedure.
- the normal force indentation depth curve indicates the rigidity of the sample during the initial period of in-situ relief.
- the maximum test force for nanoindentation is usually below 15 mN.
- a rule of thumb of 10% of the layer thickness is used. Deeper penetration curves involve an influence by the substrate used.
- the so-called multiple loading and unloading method or multi-indentation method for short.
- segmental loading and unloading are carried out on a fixed position.
- the local maximum load is continuously increased.
- various unaffected areas of the sample are also approached and tested.
- Schiffmann & Jardinr have demonstrated that there are only very small deviations between the determined values of the two methods [KI Schiffmann, RLAteilr; Comparison of Hardness and Young's Modulus by Single Indentation and Multiple Unloading Indentation. In: Journal of Metallurgy 95 (2004) 5, 31 1-316].
- the layer thickness was 1839 nm. To comply with the rule of thumb for the penetration depth of max. 10% of the layer thickness are the relief curves for the multi-indents of the example shown up to the maximum force of 0.055 mN allowed for the evaluation. For lower layer thicknesses, the associated max. to exercise local force so as not to exceed the 10% rule.
- a universal material tester UMT with nanoindentation module Nano-Head (NH2) from the company CETR (now under the company Bruker AXS S.A.S.) With appropriate vibration damping technique (minus k) used in a thermal and acoustic insulation chamber.
- UMT universal material tester
- NH2 nanoindentation module Nano-Head
- CETR now under the company Bruker AXS S.A.S.
- vibration damping technique minus k
- samples prepared according to Example 1 were measured with 10 multi-indents per site with a maximum of 0.055 mN. The multiindents have local maxima, which were then reduced to 20% of the force. These unloading curves were evaluated in the form of a tangent of 98 to 40%. 10 measurement points were tested for statistics and homogeneity.
- the removal of the measuring points was 50 ⁇ to avoid influences such as plastic deformation of the test layer by previous measurements.
- the layer thickness was 2017 nm.
- 10% of the layer thickness are the relief curves for the multi-indents of the example shown up to the maximum force of 0.055 mN allowed for the evaluation.
- the associated max. to exercise local force so as not to exceed the 10% rule.
- the maximum force for the penetration depth and the corresponding relief curve is therefore in case of doubt ⁇ 0.055 mN, it is preferred in case of layer thicknesses of ⁇ 1000 nm in case of doubt ⁇ 0.020 mN.
- Measuring example 2 XPS measurements:
- the XPS measurements are used for the determination of molar ratios for the layers according to the invention.
- the procedure is as follows:
- the XPS investigations were carried out with a VG 220i XL system (VG Scienta). Parameters: Magnetic lens mode, acceptance angle of the photoelectrons 0 °, monochromatized AIK a excitation, Constant Analyzer Energy-Mode (CAE) with 70 eV matching energy in overview spectra and 20 eV in energetically high-resolution line spectra, analysis area: 0.65 mm 0, the neutralization of electrical non-conducting samples are made with low-energy electrons (4 eV).
- the detection sensitivity of the method is element-specific and is about 0.1 at%, ie about 1000 ppm.
- the C1 s main photoemission line to be assigned to CC species is determined to be 285 eV during the evaluation, as a result of which the positions of the further photolinias shift accordingly.
- the XPS spectrometer was set up in accordance with ASTM standard E902-94.
- ASTM standard E 1078-90 was used prior to and during the analysis for sample handling.
- the standards ASTM E 996-94 and E995-95 were used to process the measured data. Applicable documents are the references named in the standards.
- the surface energy is determined in accordance with DIN 55660-2 of Dec. 201 1 using a contact angle measuring device G2 from Krüss.
- the test liquids used are water, diiodomethane and ethylene glycol with a high degree of purity.
- the test liquids have the following characteristics:
- Ethylene glycol surface energy 47.7 mN / m, polar fraction: 16.8 mN / m
- the measurement method used is the dynamic measurement (progressive contact angle), during which the contact angle is determined during the liquid supply.
- the adjustment of the baseline is done manually, horizontally in the middle between the syringe tip and the mirror image.
- the needle distance is set to approx. 2 mm.
- the surface may be cleaned with acetone (one-time very light wiping with acetone and a lint-free cloth) to reduce the risk of incorrect measurements.
- test liquid quantity 6 ⁇ with a dosage rate of 1 1, 76 ⁇ / min are used as the test liquid quantity.
- the actual measurement starts after 5 s, this corresponds to a feed volume of approx. 1 ⁇ . There are 3 drops per liquid. The respective results are averaged.
- EDX Measurement Energy dispersive X-ray spectroscopy (EDX) is a method for elementary material characterization. In this case, the sample to be examined is energetically excited by means of a primary electron beam of uniform energy. The sample relaxes by element-specific X-ray radiation is emitted, which can be analyzed with a suitable detector.
- EDX Energy dispersive X-ray spectroscopy
- the elemental analysis typically takes place from an atomic number of 6 (carbon), so that organic substances can be identified.
- 6 carbon
- low error quantitative statements may be difficult for light elements.
- This protective layer absorbs the low-energy X-ray radiation of light elements, making quantification difficult, and depending on the window material used, elements with atomic numbers of 1 1 (sodium, beryllium windows) or 6 (C, polymer-based thin windows) can be detected
- the sample space is not ventilated (such as in a transmission electron microscope) and windowless detectors can be used and so even elements up to atomic number 3 (lithium) are examined.
- TEM transmission electron microscope
- the sample thickness here is usually below 100 nm, which prevents the propagation of the excitation bulb, and the energy of the primary electron beam is several hundred keV, with the result that the primary electron beam scarcely expands as it passes through the sample.
- investigations in a scanning electron microscope (SEM) have the problem that thick samples with lower primary electron energy are usually examined here.
- the low energy of the electrons leads to a rapid Auffäub- tion of the primary electron beam under the sample surface and the thickness of the sample allows the excitation bulb to completely emboss.
- a sample thin section (a TEM lamella) with a final sample thickness of less than 100 nm is first produced using the Focused Ion Beam Method (FIB).
- FIB Focused Ion Beam Method
- a protective layer of carbon and platinum is applied beforehand by means of EBID ("electron beam induced deposition") and IBID (Jon Beam Induced Deposition) in the corresponding area.
- the EDX examination is carried out in the TEM.
- the Tecnai TF-20 S-Twin G 2 transmission electron microscope manufactured by FEI Hillsboro, Oregon
- the microscope was then used in scanning mode electron microscopy (STEM) with a spot size of about 1-2 nm
- STEM scanning mode electron microscopy
- the detector used was an EDAX r-TEM EDX detector with S-UTW window ("super ultrathin window”), whose resolution is 136eV.
- FIG. 4a shows a line profile on the surface of an electropolished 1.4404 steel surface (after laser treatment).
- the starting point position 0 nm
- the starting point is marked with a cross in the STEM image in FIG. 4a.
- FIGS. 4b and 4c illustrate the measurement results.
- a line profile created by means of EDX measurements (see FIG. 4a) of an electropolished 1.4404 steel sample before the laser treatment shows only a thin oxide layer (about 5 nm, dark area in the middle of FIG. 4a) directly at the surface.
- the iron content decreases slightly to about 40 at%, whereas the carbon content increases to about 30 at%.
- Above the oxide layer there is a marked increase in the carbon and platinum signals, which is due to the protective layer necessary for the FIB preparation.
- the sample which was additionally subjected to a laser treatment with the parameter 2 of the embodiment 1, significant changes.
- the oxide layer thickness has grown by the treatment to about 16 nm.
- 5a shows a line profile on the surface of an electropolished 1.4404 steel surface (after laser treatment). The starting point (position 0 nm) is marked with a cross in FIG. 5a.
- FIGS. 5b and 5c illustrate the measurement results.
- the stainless steel used (X2CrNiMo17-12-2, 1.4404, V4A) is one of the common corrosion-resistant stainless steel grades. Its molybdenum content is characterized by its high resistance to non-oxidizing acids and halogen-containing media. In addition, this material is easy to process and can be used at temperatures of up to 550 ° C. In terms of corrosion resistance (especially in the presence of chlorides), this material is also significantly better than, for example, the molybdenum additive. the commonly used stainless steel X5CrNi18-10, 1.4301 (V2A). Stainless steel 1.4404 shows excellent corrosion resistance in natural environmental media and industrial areas with moderate chlorine and salt concentrations as well as in the food and pharmaceutical industries. Due to the low carbon content, the material is resistant to intercrystalline corrosion according to DIN EN ISO 3651 Part 2.
- stainless steel 1.4404 is not seawater resistant. Thus, it is initially not suitable for sophisticated corrosion protection applications. This is confirmed by the following Table 1 with laboratory experiments (optimal sample body) of the manufacturer Deutsche Brasswerke. [Material Data Sheet Acidur 4404 of Manual Austechnike, 16/10/2015 2015-0016] Attack concentration Concentration Temperature resistance
- the material is first subjected to a laser treatment, wherein proposed for further surface optimization, but not required to smooth the workpiece surface first by means of electropolishing. This may generally be preferred in the sense of the invention.
- a CL250 device from the company Clean-Lasersysteme GmbH with a power of the beam source of 250 W is used.
- the diode-pumped Nd: YAG laser (short for neodymium-doped yttrium-aluminum garnet as active medium) emits infrared radiation at a wavelength of 1064 nm.
- the system has a Q-switch Q-switching, the pulse repetition frequencies of 10 to 40 kHz, and pulse lengths of at least 80 to 200 ns allowed.
- the resulting maximum pulse energy of this system is thus 21 mJ.
- the laser parameters used were:
- Parameter 1 Power: 250 W, pulse repetition frequency: 12 kHz, pulse duration: 100 ns, scanning in x-direction, scanning speed: 2050 mm / s, overlap: 75%, fluence: 5 J / cm 2 , repetitions: 2
- Parameter 2 power: 165 W, pulse repetition frequency: 12 kHz, pulse duration: 100 ns, scanning speed: 2050 mm / s, overlap: 75%, fluence: 3.8 J / cm 2 , repetitions: 2, scanning in x and y-direction
- the samples which had changed color by the laser treatment were provided with a plasma polymer corrosion protection layer according to the invention according to DE102013219337.
- a Plasmapolymerisationsstrom was used with a volume of about 1 m 3.
- the system is characterized by its large electrode surface about 3m 2 , which thus corresponds approximately to the surface of the electrical ground.
- the samples were brought into high frequency contact with the electrode.
- a working pressure of 0.018 mbar was set with the working gases hexamethydisiloxane and oxygen, after previously with pure oxygen, a pre-cleaning of the surface took place.
- a high frequency power of 1200 W was coupled into the electrodes.
- the gases were used in a 2: 1 ratio with a total of 135 sccm.
- the layer thickness produced was 0.55 ⁇ , the modulus of elasticity 1, 3 GPa, the surface energy 23.5 mN / m with a polar content of Wu of 0.85 mN / m.
- a stainless steel 1.4404 is subjected to a laser treatment according to Example 1.
- a CL100 unit from Clean-Lasersysteme GmbH with a power of 100 W is used.
- Laser emits laser radiation with a wavelength of 1064 nm, with a pulse repetition frequency of 100 to 200 kHz and a pulse length of 80 ns (with a pulse energy of 1 mJ).
- the resulting maximum pulse energy of the system is 12.7 J / cm 2 .
- the laser parameters used were: Parameter 3: Power: 20 W; Pulse repetition frequency: 200 kHz; Pulse duration: ⁇ 100 ns; Scanning speed: 2000 mm / s; Overlap: 90%; Fluence: 1.3 J / cm 2 ; Repetitions 3
- Parameter 4 power: 25 W; Pulse repetition frequency: 200 kHz; Pulse duration: -100 ns; Scanning speed: 2500 mm / s; Overlap: 87.5; Fluence: 1.6 J / cm 2 ; Repetitions 8
- Parameter 5 power: 30 W; Pulse repetition frequency: 200 kHz; Pulse duration: -100 ns; Scanning speed: 3000 mm / s; Overlap: 85%; Fluence: 1.9 J / cm 2 ; Repetitions 8
- the samples which had changed in color by the laser treatment were provided with a plasma polymer corrosion protection layer according to the invention according to DE102013219337 (corresponding to the procedure described and US Pat Coating in Example 1).
- the layer thickness produced was 0.55 ⁇ , the modulus of elasticity 1, 3 GPa, the surface energy 23.5 mN / m with a polar content of Wu of 0.85 mN / m.
- EDX energy dispersive X-ray spectroscopy
- TEM Transmission Electron Microscope
- FIB focused ion beam
- the element composition was observed at different locations in the near-surface region, with the oxygen content decreasing with increasing distance from the surface.
- the sample which was additionally subjected to the laser treatment, changes (see Fig. 2a) - c.)).
- the oxide layer thickness has grown by the treatment to about 16 nm. In the oxide are almost no iron, no molybdenum, no silicon and no nickel (only in the bulk near area) more. In contrast, chromium and manganese together with oxygen is significantly enriched. There are corresponding oxides have formed. These promote the corrosion stability and, apparently, the adhesion of the plasma-polymer layer to be used.
- Table 5 XPS surface composition of differently treated surfaces of the material 1.4404
- the result can be interpreted in such a way that laser treatment in particular reduces the near-surface iron, nickel and molybdenum content. At the same time, oxidation of the remaining elements (especially chromium and manganese) takes place. The oxide layer thickness increases significantly. Since the heat input is very low and only limited to the surface, no iron migrates from the bulk area. It comes surfaces close to a significant iron oxide depletion.
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Abstract
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DE102016213023.4A DE102016213023A1 (de) | 2016-07-15 | 2016-07-15 | Substrat mit Korrosionsschutzsystem |
PCT/EP2017/066439 WO2018010987A1 (de) | 2016-07-15 | 2017-07-03 | Substrat mit korrosionsschutzsystem |
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JP2788246B2 (ja) | 1988-03-25 | 1998-08-20 | 株式会社東芝 | 材料の表面処理方法およびその表面処理装置 |
EP0625588B1 (de) * | 1993-05-21 | 2001-10-24 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Plasmapolymer-Schichtenfolge als Hartstoffschicht mit definiert einstellbarem Adhäsionsverhalten |
JP3428175B2 (ja) | 1994-10-05 | 2003-07-22 | 株式会社日立製作所 | 表面処理層を有する構造物および表面処理層の形成方法 |
EP1722006A1 (de) * | 2005-05-10 | 2006-11-15 | S.I.C.C. Societa' Per Azioni | Verfahren zur korrosionsschutzenden Oberflächebehandlung von Behälter für Flüssigkeiten, dadurch erhaltene Behälter und Vorrichtung zur Ausführung des Verfahrens |
RU2287414C1 (ru) | 2005-05-27 | 2006-11-20 | Общество с ограниченной ответственностью "Лазерный Центр" | Способ лазерной модификации поверхности металла или его сплава |
DE102009007100A1 (de) * | 2009-02-02 | 2010-08-05 | Thyssenkrupp Steel Europe Ag | Stahlflachprodukt mit einem metallischen Überzug und Verfahren zu seiner Herstellung |
KR100964574B1 (ko) | 2009-07-23 | 2010-06-21 | 주식회사 에스코넥 | 금속 소재의 표면에 대한 레이저 컬러 마킹방법 |
DE102013210176B3 (de) * | 2013-05-31 | 2014-09-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Laser-Prozess zur Erzeugung von Beschichtungen auf Leichtmetall(legierungen) sowie resultierende Beschichtungen und Produkte |
DE102013219337B3 (de) | 2013-09-25 | 2015-04-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, deren Herstellung sowie deren Verwendung als Korrosionsschutz |
DE102013219331B3 (de) * | 2013-09-25 | 2015-03-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, sowie deren Verwendung |
DE102014015474A1 (de) * | 2014-10-18 | 2016-04-21 | Daimler Ag | Beschichtete Bremsscheibe und Herstellungsverfahren |
CN104911329A (zh) | 2015-05-28 | 2015-09-16 | 湖北工业大学 | 一种利用超短脉冲激光制备不锈钢超疏水耐腐蚀表面的方法 |
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