EP3129527A1 - Method for passivating a metal surface - Google Patents
Method for passivating a metal surfaceInfo
- Publication number
- EP3129527A1 EP3129527A1 EP15712058.5A EP15712058A EP3129527A1 EP 3129527 A1 EP3129527 A1 EP 3129527A1 EP 15712058 A EP15712058 A EP 15712058A EP 3129527 A1 EP3129527 A1 EP 3129527A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- component
- light metal
- conversion layer
- concentration
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002161 passivation Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 150000001413 amino acids Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 5
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 82
- 238000000576 coating method Methods 0.000 claims description 51
- 239000011248 coating agent Substances 0.000 claims description 35
- 239000003973 paint Substances 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229940024606 amino acid Drugs 0.000 claims description 9
- 235000001014 amino acid Nutrition 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000008280 blood Substances 0.000 claims description 8
- 210000004369 blood Anatomy 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 6
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 6
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 6
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 6
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 6
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 6
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 claims description 6
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- FAPWYRCQGJNNSJ-UBKPKTQASA-L calcium D-pantothenic acid Chemical compound [Ca+2].OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O.OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O FAPWYRCQGJNNSJ-UBKPKTQASA-L 0.000 claims description 5
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 4
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 4
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 4
- 229960000367 inositol Drugs 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035515 penetration Effects 0.000 claims description 4
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 4
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims description 3
- 229930064664 L-arginine Natural products 0.000 claims description 3
- 235000014852 L-arginine Nutrition 0.000 claims description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 3
- 235000019393 L-cystine Nutrition 0.000 claims description 3
- 239000004158 L-cystine Substances 0.000 claims description 3
- 235000019454 L-leucine Nutrition 0.000 claims description 3
- 239000004395 L-leucine Substances 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- 229930195722 L-methionine Natural products 0.000 claims description 3
- 239000004473 Threonine Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229960003067 cystine Drugs 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 229960002885 histidine Drugs 0.000 claims description 3
- 229960003136 leucine Drugs 0.000 claims description 3
- 229960004452 methionine Drugs 0.000 claims description 3
- 229960005190 phenylalanine Drugs 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 229960001153 serine Drugs 0.000 claims description 3
- 229960002898 threonine Drugs 0.000 claims description 3
- 229960004799 tryptophan Drugs 0.000 claims description 3
- 229960004441 tyrosine Drugs 0.000 claims description 3
- 229960004295 valine Drugs 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims description 2
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960000304 folic acid Drugs 0.000 claims description 2
- 235000019152 folic acid Nutrition 0.000 claims description 2
- 239000011724 folic acid Substances 0.000 claims description 2
- 229960003966 nicotinamide Drugs 0.000 claims description 2
- 235000005152 nicotinamide Nutrition 0.000 claims description 2
- 239000011570 nicotinamide Substances 0.000 claims description 2
- 229960002477 riboflavin Drugs 0.000 claims description 2
- 235000019192 riboflavin Nutrition 0.000 claims description 2
- 239000002151 riboflavin Substances 0.000 claims description 2
- 229960003495 thiamine Drugs 0.000 claims description 2
- RADKZDMFGJYCBB-UHFFFAOYSA-N Pyridoxal Chemical compound CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 claims 1
- 229960003581 pyridoxal Drugs 0.000 claims 1
- 235000008164 pyridoxal Nutrition 0.000 claims 1
- 239000011674 pyridoxal Substances 0.000 claims 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 16
- 238000007591 painting process Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 4
- 229930182844 L-isoleucine Natural products 0.000 description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 4
- 229960000310 isoleucine Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000001962 electrophoresis Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000019766 L-Lysine Nutrition 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- -1 amino acids D-Ca-pantothenate Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
Definitions
- the invention relates to a method for passivating a metallic surface of a light metal component according to the preamble of
- the use of light metal components is industry-standard practice.
- vehicle construction for example, vehicle bodies in mixed construction, for example, made of light metal and sheet steel parts to achieve a weight reduction.
- aluminum or magnesium materials or alloys thereof can be used as the light metal.
- the provided with the primer vehicle body is led to another coating station in which a top coat is done in the desired color by the customer.
- the paint particles can be transported by an electrostatic field of high voltage standing support heads to the grounded body.
- This topcoat is also followed by a continuous furnace in which curing of the topcoat takes place at high temperature.
- a clearcoat is applied in a further coating station, which is also cured at high temperature in a subsequent drying step.
- the light metal components are more susceptible to corrosion than the steel components. Especially paint undercuts and filiform corrosion are more common damage patterns.
- a pickling passivation and the application of an anodic coating is common practice.
- the commercial coatings only partially provide the necessary protective effect against self-corrosion, filiform corrosion and / or paint infiltration.
- the high potential difference should be regarded as promoting corrosion.
- the commercially available coating systems for light metal components do not exhibit sufficient passivating behavior and are often too "noble” (ie too high a corrosion potential), especially with respect to magnesium more noble metals (for example, aluminum) electrochemically polarized, there is an exponential increase in the corrosion current.
- the object of the invention is to provide a method for passivating the metallic surface of a light metal component, in which, in particular with aluminum or magnesium, a sufficient passivation is achieved and a contact corrosion risk is reduced.
- the invention is based on the idea of orienting the composition of the passivation solution, at least in principle, to the composition of human blood. Surprisingly, it has been found that certain components of human blood produce a protective and passivating coating on metal surfaces, especially of light metal such as aluminum and / or magnesium. In a specific embodiment of the invention, concentrations of individual constituents can be simulated essentially unchanged in the passivation solution.
- a special Passivitations Colour in which using an aqueous, especially blood-like passivation on the metallic component surface a calcium phosphate-containing conversion layer is generated, the oxides and hydroxides of the component material and the passivation solution and contains amino acids ,
- the light metal component formed with the passivated metallic surface can be used across industries.
- the light metal component can be applied in the medical field.
- the light metal component may optionally be used in the automotive sector, and that is visible within the vehicle or as externally visible outer part.
- the light metal component can be realized as a vehicle-inner-side display frame, an aggregate part, a chassis part or a component of a seat frame structure.
- the passivating anticorrosive primer (ie the conversion layer) produces a reduction of the self-corrosive currents by a factor of 10.
- the pitting potential is increased by more than 0.5 V with a simultaneous reduction of the cathodic current densities.
- the conversion layer according to the invention is very favorably in contact with nobler materials (such as aluminum or steel).
- nobler materials such as aluminum or steel.
- there is an increase in the penetration resistance by application of the coating that is, the higher the penetration resistance, the lower the corrosion currents, the penetration resistance behaves inversely proportional to the corrosion currents).
- the conversion layer according to the invention generates low intrinsic corrosion currents and high passivity. In contact with aluminum and steel, only small contact corrosion currents result.
- the passivation solution results in a compact calcium phosphate and aluminum hydroxide / oxide-containing coating with amino acids.
- the layer morphology is constructed in the form of a lobe, with intermediate cracks which, for example, provide a sufficiently large residual conductivity in the case of a subsequent KTL deposition in a painting process.
- the liquid starting component of the primer can penetrate into the cracks, resulting in good adhesion between the conversion layer and the primer.
- a compact calcium phosphate and magnesium hydroxide / oxide-containing coating is obtained, the layer morphology of which is also formed in a lump-shaped manner.
- the passivation solution may preferably have at least the following constituents as activators for activating the metal surface of the component:
- NaCl with a concentration between 5500 and 7500, in particular
- KCl with a concentration between 300 and 500, in particular
- the passivation solution may have at least the following amino acids as catalysts and layer formers:
- the amino acid L-isoleucine acts specifically as a layering agent that supports the adhesion of the conversion layer on the metallic component surface.
- the passivation layer may preferably contain calcium phosphates.
- the conversion layer may contain carbonaceous constituents.
- the passivation solution may contain NaHCO 3 .
- the carbonate formation is also dependent on possibly supplied C0 2 .
- the passivating solution may contain Na pyruvate, with a concentration between 90 and 150 mg / l, in particular 110 mg / l.
- an essential aspect of the invention is that certain components of human blood are transferred to the passivation solution in substantially unchanged concentrations.
- the aqueous passivating solution may contain at least the following constituents, the concentrations of which are reproduced in their concentrations in human blood:
- NaHCQ 3 with in particular 3700 mg / l Na pyruvate with in particular 110 mg / l
- the passivation reaction according to the invention can be carried out at a pH of about 7. In this case, the coating reaction is slow. Alternatively, the coating reaction can also be in the acidic range occur. The coating reaction can be accelerated by increasing the temperature, - reducing the pH and / or by polarization and / or increasing the partial pressure of C0 2 .
- the light metal component may be a vehicle part, which is first pretreated with the passivation solution according to the invention to form the conversion layer. The conversion layer of the component can be covered with at least one further layer in a subsequent coating process.
- the coating process may comprise a first coating step in which a light metal KTL layer, ie an organic protective layer, is formed. This is done in a dipping process (ie light metal KTL) under applied DC voltage, whereby the paint particles dissolved in the immersion bath are attracted to the metallic component and remain there to form the light metal KTL layer.
- a powder coating is then applied. This is done in a powder coating process with applied DC voltage.
- the special clod-shaped layer morphology with the crack structures already mentioned above is of particular importance. This ensures namely in the dipping process and in the powder coating process sufficient electrical residual conductivity through the conversion layer.
- the light metal component for example as a visible outer part
- the body shell is then subjected to a conventional body painting process together with the light metal component mounted thereon. That is, there is a cataphoresis primer of the body shell in immersion process, in which under applied electrical DC voltage dissolved in the immersion paint particles are attracted to the body shell and stick there to form a primer.
- the primed body shell is conveyed into a downstream continuous furnace, in which the primer is baked.
- the green body provided with the primer is led to another coating station in which a KTL process takes place.
- the KTL process is also followed by a continuous furnace in which the KTL layer burns in at high temperatures.
- a conventional automotive paint system is applied, which is also baked in a subsequent drying step at high temperature.
- the light metal component mounted on the green body is already precoated with a layer structure, namely with the conversion layer, the light metal KTL layer and the powder coating.
- the light metal component is thus electrically insulated, so that the electroplated in the bodyshell painting process KTL layer no longer adhere, while the conventional automotive paint system can be easily applied to the already coated light metal component.
- 1 shows the layer structure of a finished painted light metal component, which is intended to represent here an example externally attachable to the vehicle body outer part.
- Figs. 2 to 4 are respective flowcharts illustrating coating processes for producing the layer structure shown in Fig. 1;
- the layer structure 1 of a paint coating on the metal surface 25 of a body component 3 is shown by way of example in a greatly enlarged partial sectional view.
- the body part 3 made of light metal, such as aluminum, magnesium or an alloy thereof.
- the conversion layer 5 is coated by a light metal KTL layer 6.
- a powder coating 7 is formed, on which a conventional automotive paint system 9 is applied.
- the conversion layer 5 has a clod-shaped layer morphology, in which cracks 13 are formed between individual blocks 11.
- the cracks 13 provide in a KTL coating process described later for a sufficient residual conductivity between a cathodic dip bath and the light metal material of the component 3.
- the liquid starting component of the light metal KTL layer 6 penetrate into the cracks 13 and thereby increase the adhesive bond to the conversion layer 5.
- Fig. 1 As well as the other Figs. 2 to 7, are made with a view to a simpler understanding of the invention. Therefore, the figures are only roughly simplified representations that do not reflect a realistic layer structure 1.
- the conversion layer 5 actually has a layer thickness which lies in the ⁇ range. 2 to 4, a series lacquer process carried out in a lacquering plant is described, in which a passivation solution according to the invention is used: Accordingly, a passivation step P (FIG. 2) first follows. In the passivation step P, a degreasing, grinding and / or pickling of the component 3 is performed. The thus cleaned component 3 is then subjected to a passivation according to the invention, in which it is immersed in an immersion bath of the passivation solution.
- composition of the aqueous passivating solution is basically based on the composition of human blood.
- the passivation solution contains at least the following
- NaCl and KCl in the passivation solution serve to activate the metal surface 25.
- the amino acids D-Ca-pantothenate and myo-inositol are mainly responsible for the coating process and also have a catalyzing effect.
- the components NaH 2 P0 4 and CaCl 2 support the coating process by incorporating the Ca 2+ and P0 4 3 " ions into the conversion layer 5.
- the conversion layer 5 according to the invention also has carbonate-containing layer constituents. These are provided in the passivation solution by the component NaHC0 3 and C0 2 (from the atmosphere). Another component used for layer formation is the component Na pyruvate.
- L-serine m 142 mg / l L-serine m 142 mg / l.
- the above amino acids are also components of human blood whose concentrations are almost unchanged.
- the passivation solution according to the invention is an aqueous treatment liquid whose pH is in the range of about 7 or in the acidic range.
- the passivation takes place in the immersion bath at a treatment temperature in the range of 18 to 25 ° C.
- the treatment time depends on the set pH value, the process temperature and optionally an additional polarization as well as the required nominal thickness of the coating.
- the component 3 is fed to a rinsing / drying process.
- the component 3 coated with the conversion layer 5 is provided in the further process sequence (according to FIG. 3) in a coating station 17 with a light metal KTL layer 6 (i.e., an organic protective layer).
- the light metal KTL is carried out in common practice in the dipping process in which an electrical DC voltage is applied between the body 1 and the dip tank, whereby the dissolved in the dipping bath paint particles are attracted to the component 3 and adhere there evenly. Additionally required pre- or post-treatment steps are omitted for the sake of easier understanding of the invention.
- the component 3 passes through a continuous furnace at a predetermined conveying speed, in which the light metal KTL layer 6 is baked at process temperatures in the range of, for example, 180 ° C.
- a powder coating is applied, in which the layer 7 (FIG. 1) is applied to the component 3.
- the paint particles are under tension by an electrostatic field standing pointed heads transported to the grounded component 3.
- a further drying station 19 again a baking process in a continuous furnace.
- the component coating process L ie process steps I and II of FIG.
- the light metal component 3 is joined in a riveting process to a shell body 15 which has not yet been painted, in an exemplary possible application as a visible vehicle exterior part.
- the green body 15 is conveyed in a continuous process in a body painting plant (see Fig. 4).
- the primed shell body 15 is conveyed to a downstream continuous furnace 27, in which the primer is baked.
- the green body 15 provided with the primer is led to a further coating station 29, in which a KTL process takes place.
- the KTL process 29 is likewise followed by a continuous furnace 31, in which the coating is baked at high temperature. Subsequently, in a further coating station 33, a conventional automotive four-layer paint system 9 is applied, which is subsequently subjected to a baking process 35.
- the body painting process shown in FIG. 4 is carried out with already pre-coated light metal component 3. That is to say that the light metal component 3 is electrically insulated, so that the cathodic electrocoating layer applied in the bodyshell painting process no longer adheres, whereas the conventional automobile paint system 9 (ie a four-layer structure) can be readily applied to the powder coating 7 of the light metal component 3.
- the light metal component 3 is shown in different process steps in views corresponding to FIG. 1.
- the light metal component 3 with cleaned and exposed metallic surface 25 is shown.
- Fig. 6 the light metal component 3 is shown after passivation and outsourcing.
- the conversion layer 5 is applied to the metallic surface 25 of the light metal component, namely with the Schollenmorphologie invention, ie with clod-like individual fragments 11 and intermediate cracks 13.
- Fig. 7 is the light metal component 3 after the light metal KTL process shown, in which the starting component of the light metal KTL layer 6 soaks through the crack structure 13 of the conversion layer 5, whereby the adhesive bond between the conversion layer 5 and the light metal KTL layer 6 is substantially increased.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102014005444.6A DE102014005444A1 (en) | 2014-04-11 | 2014-04-11 | Method for passivation of a metallic surface |
PCT/EP2015/000622 WO2015154851A1 (en) | 2014-04-11 | 2015-03-21 | Method for passivating a metal surface |
Publications (2)
Publication Number | Publication Date |
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EP3129527A1 true EP3129527A1 (en) | 2017-02-15 |
EP3129527B1 EP3129527B1 (en) | 2019-08-28 |
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EP15712058.5A Active EP3129527B1 (en) | 2014-04-11 | 2015-03-21 | Method for passivating a metal surface |
Country Status (6)
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US (1) | US10351959B2 (en) |
EP (1) | EP3129527B1 (en) |
CN (1) | CN106164343B (en) |
DE (1) | DE102014005444A1 (en) |
ES (1) | ES2747966T3 (en) |
WO (1) | WO2015154851A1 (en) |
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DE102016002852A1 (en) | 2016-03-10 | 2017-09-14 | Audi Ag | Method for passivating a surface of a metal component |
DE102017107529A1 (en) * | 2017-04-07 | 2018-10-11 | Lisa Dräxlmaier GmbH | Process for corrosion inhibition of metals and tempering system for a metallic tool |
CN107419257A (en) * | 2017-07-04 | 2017-12-01 | 安徽腾龙泵阀制造有限公司 | A kind of surface passivating treatment technique of galvanized steel plain sheet |
DE102017011379A1 (en) | 2017-12-11 | 2019-06-13 | Audi Ag | Anti-corrosion coating for metallic substrates |
DE102021134434B4 (en) | 2021-12-23 | 2023-08-03 | Audi Aktiengesellschaft | Process arrangement and method for treating a metal component |
Family Cites Families (15)
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BE515434A (en) * | 1951-11-19 | |||
DE1072055B (en) * | 1952-08-28 | |||
DE4417965A1 (en) * | 1994-05-21 | 1995-11-23 | Henkel Kgaa | Iron phosphating using substituted monocarboxylic acids |
DE19630289C2 (en) | 1996-07-26 | 2002-03-14 | Audi Ag | Process for painting vehicle bodies |
DE19939519A1 (en) * | 1999-08-20 | 2001-02-22 | Henkel Kgaa | Acidic aqueous phosphating solution for treating steel surfaces contains zinc ions, phosphate ions, and organic nitro-compound(s) as accelerator selected from nitroarginine (derivatives) and 5-nitro-2-furfurylidenedicarboxylates |
FI20010523A0 (en) * | 2001-03-16 | 2001-03-16 | Yli Urpo Antti | Treatment of sols, gels and mixtures thereof |
JP4230983B2 (en) * | 2004-11-17 | 2009-02-25 | 大日本塗料株式会社 | Anticorrosion paint composition |
US20080097618A1 (en) | 2006-10-18 | 2008-04-24 | Kevin Charles Baker | Deposition of calcium-phosphate (CaP) and calcium-phosphate with bone morphogenic protein (CaP+BMP) coatings on metallic and polymeric surfaces |
CN100588743C (en) | 2007-04-09 | 2010-02-10 | 比亚迪股份有限公司 | A kind of acidic solution and treatment process that is used to handle Mg alloy surface |
JP4750096B2 (en) * | 2007-11-07 | 2011-08-17 | 株式会社新技術研究所 | Magnesium alloy article, magnesium alloy member and manufacturing method thereof |
KR101233279B1 (en) * | 2010-08-06 | 2013-02-14 | 설영택 | Surface metal oxides for implants, implants or devices using the same and method for producing the implants or devices |
DE102010048385A1 (en) | 2010-10-13 | 2012-04-19 | Audi Ag | Device for connecting a vehicle to a socket |
DE102010060700B4 (en) * | 2010-11-22 | 2023-03-16 | Dr. Ing. H.C. F. Porsche Aktiengesellschaft | Body shell construction and method for producing the same |
CN102690558B (en) | 2012-05-31 | 2013-05-29 | 蓬莱蔚阳新材料有限公司 | Process for preparing rust-bearing rust-proof heavy-duty coating |
US9469677B2 (en) * | 2013-11-13 | 2016-10-18 | University of Pittsburgh—of the Commonwealth System of Higher Education | Biomimetic coating of magnesium alloy for enhanced corrosion resistance and calcium phosphate deposition |
-
2014
- 2014-04-11 DE DE102014005444.6A patent/DE102014005444A1/en not_active Withdrawn
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2015
- 2015-03-21 US US15/303,376 patent/US10351959B2/en active Active
- 2015-03-21 WO PCT/EP2015/000622 patent/WO2015154851A1/en active Application Filing
- 2015-03-21 EP EP15712058.5A patent/EP3129527B1/en active Active
- 2015-03-21 ES ES15712058T patent/ES2747966T3/en active Active
- 2015-03-21 CN CN201580018917.7A patent/CN106164343B/en active Active
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ES2747966T3 (en) | 2020-03-12 |
EP3129527B1 (en) | 2019-08-28 |
CN106164343A (en) | 2016-11-23 |
CN106164343B (en) | 2018-09-11 |
US20170037517A1 (en) | 2017-02-09 |
US10351959B2 (en) | 2019-07-16 |
DE102014005444A1 (en) | 2015-10-15 |
WO2015154851A1 (en) | 2015-10-15 |
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