EP3230491A1 - Réception de métaux légers dans un procédé de prétraitement et de décapage de l'acier - Google Patents
Réception de métaux légers dans un procédé de prétraitement et de décapage de l'acierInfo
- Publication number
- EP3230491A1 EP3230491A1 EP15804762.1A EP15804762A EP3230491A1 EP 3230491 A1 EP3230491 A1 EP 3230491A1 EP 15804762 A EP15804762 A EP 15804762A EP 3230491 A1 EP3230491 A1 EP 3230491A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- components
- iron
- bath solution
- aluminum
- reaction
- 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
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title description 20
- 239000002184 metal Substances 0.000 title description 19
- 238000005554 pickling Methods 0.000 title description 10
- 229910000831 Steel Inorganic materials 0.000 title description 6
- 150000002739 metals Chemical class 0.000 title description 6
- 239000010959 steel Substances 0.000 title description 6
- 230000010354 integration Effects 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052742 iron Inorganic materials 0.000 claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 235000021110 pickles Nutrition 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000000126 substance Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- -1 iron ions Chemical class 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000005238 degreasing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 abstract 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 55
- 238000004519 manufacturing process Methods 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 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 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910007828 Li2ZrF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- WVRFOMOBQZOCAI-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Zn+].[Fe+2] Chemical group P(=O)([O-])([O-])[O-].[Zn+].[Fe+2] WVRFOMOBQZOCAI-UHFFFAOYSA-K 0.000 description 1
- 229910010165 TiCu Inorganic materials 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical class [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical group [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
- MFFVROSEPLMJAP-UHFFFAOYSA-J zirconium(4+);tetraacetate Chemical class [Zr+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O MFFVROSEPLMJAP-UHFFFAOYSA-J 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
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/34—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 fluorides or complex fluorides
-
- 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
- C23C22/73—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 characterised by the process
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/081—Iron or steel solutions containing H2SO4
Definitions
- the present invention relates to a process for wet-chemical pretreatment of a plurality of iron components and a plurality of aluminum components in series.
- iron components especially steel components, processed and manufactured.
- these components are pickled and applied a conversion layer.
- the components undergo established production lines with a specific sequence of different immersion baths, which are adapted to the chemical composition of the iron components.
- more and more iron components are replaced by components made of light metal such as aluminum or magnesium.
- the production lines designed for iron components can not pass through light metals such as aluminum or magnesium because of their properties other than iron.
- certain dipping baths which are integrated into production lines for iron components and adapted to these components, a very low pH (pH ⁇ 1), so that when passing through such baths, the etching of the light metal components is too large.
- the invention relates in a first aspect to a process for the wet-chemical pretreatment of a plurality of iron components and a plurality of aluminum components in series, in which each of the iron components passes through first a pickle (1) and subsequently a reaction nozzle (2), successively each of the aluminum components also undergoes the same reaction rinse (2) but without having undergone a pickle (1), the method being characterized in that the pickle (1) is contacted by contacting with a sulfuric acid aqueous bath solution (A) a pH below 1, 0 and the reaction rinse (2) by contacting with a sulfuric acid aqueous bath solution (B), the total of at least 0.02 g / kg of water-soluble compounds of the elements zirconium and / or titanium, respectively based on the respective elements and their pH is not less than 1, 0 takes place.
- A sulfuric acid aqueous bath solution
- B sulfuric acid aqueous bath solution
- the entrained bath solution (A) and the iron ions contained therein have an advantageous effect on the reaction rinse (2), since the iron ions accelerate the formation of the conversion layer on the light metal components and the bath solution (A) the bath solution (B) also acidified, ie an advantageous pH in the bath solution (B) can keep constant or at least contributes to the maintenance of the advantageous pH, but this does not fall below a value of 1, 0. It has surprisingly been found that a relatively high content of iron ions in the bath solution (B) of up to 10 g per kg bath solution (B) has no negative effect on the bath solution (B) or on the formation of the conversion layer on the light metal components ,
- the pretreatment according to the invention serves to apply a corrosion-protecting first coating as a primer for organic coatings.
- the pretreatment therefore always ends with the application of a first organic coating (primer, dip paint, powder coating), which itself is not a pretreatment step in the sense of the present invention.
- a "variety" as used herein refers to 2 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 100, 200, 300, 400 or more.
- the inventive method relates to a wet chemical pretreatment of a plurality of iron components and a plurality of aluminum components in series.
- pretreatment in series is the bringing into contact of a large number of components with bath solutions stored in system tanks for pickle (1) and / or reaction blister (2) and / or further wet chemical treatment steps, wherein the individual components are brought into contact one after the other and thus separated in time.
- wet-chemical describes that a change in the chemical finish of at least one of the metallic surfaces of the component to be treated is effected by contact with a liquid, which liquid is usually substantially water then "wet-chemically", if during its course at least one contacted with the liquid, metallic surfaces undergoes a pickling of at least 0.5 g / m 2 or the liquid at least 10 g / kg of organic compounds having a molecular weight of at least 100 g contains / mol or a significant surface coverage is effected with metallic or semi-metallic foreign elements.
- Foreign elements in this context are metallic or semi-metallic elements whose surface portion in the contact area of the component with the liquid immediately before contacting is less than 5 At .-% measured by X-ray photoelectron spectroscopy (Al- ⁇ radiation and 54.7 ° angle between the beam incidence and the detector A significant surface coverage is in any case present if the proportion of metallic or semi-metallic foreign elements on at least one metallic surface of the component immediately after the treatment step is greater than 1 mg / m 2 based on the respective foreign element Pickling (1) or reaction (2) are therefore typical wet-chemical treatment steps as well as activation (3) and phosphating (4).
- the iron components used according to the method essentially have surfaces of steel and / or iron, preferably more than 60%, particularly preferably more than 80%, particularly preferably more than 90% of all metallic surfaces of the iron components are surfaces of steel and / or iron.
- all metallic surfaces of the iron components are surfaces of steel and / or iron.
- the iron component may optionally contain additives of other metals and / or non-metals. These additives may be selected from the group comprising carbon, silicon, chromium, nickel, manganese, molybdenum, tungsten, and mixtures of the foregoing, but the group is not limited thereto.
- Aluminum members as used herein have substantially surfaces of aluminum and / or aluminum alloys, preferably more than 60%, more preferably more than 80%, most preferably more than 90% of all metallic surfaces of the Aluminum components Surfaces of aluminum and / or its alloys. In a particularly preferred embodiment of the method according to the invention, all metallic surfaces of the aluminum components are surfaces of aluminum and / or its alloys.
- the aluminum components may optionally include additives of other metals and / or non-metals. Such additives may be selected from the group comprising silicon, beryllium, magnesium, copper, nickel, zinc, manganese and mixtures of the foregoing, but the group is not limited thereto.
- each of the iron components passes immediately after a pickle (1) and then a reaction rinse (2), whereas each of the aluminum components through the same reaction rinse (2), but without having the stain (1) to go through.
- Process steps for a component in the context of serial pretreatment then follow each other "directly" if they are not interrupted by another than the respectively provided subsequent wet-chemical treatment or a rinsing step.
- the stain (1) is made by contacting the iron component with a sulfuric acid bath solution (A) having a pH below 1, 0.
- the pH is in the range of 0 to ⁇ 1.
- the bath solution (A) contains water as the main component and sulfuric acid to adjust the desired pH.
- pH corresponds to the negative decadic logarithm of the hydronium ion activity at 20 ° C and can be determined by pH-sensitive glass electrodes.
- the plurality of iron components is pickled, wherein on the surface of the component iron in the form of iron ions goes into solution.
- the bath solution (A) of the stain (1) has a free acid content in points of at least 50, more preferably of at least 130 to 200, but preferably of not more than 400.
- the "free acidity" in points is determined in accordance with the consumption of 0.1 N sodium hydroxide solution in milliliters until a pH of 4.0 at a withdrawn volume of the respective bath solution of 10 ml and a dilution in the ratio of 1: 5 ,
- the stain (1) contains not more than 80 g / kg, preferably not more than 60 g / kg of iron ions, but preferably at least 1.0 g / kg of iron ions in each case based on the bath solution (A).
- the reaction rinse (2) is carried out by bringing the component into contact with a sulfuric acid bath solution (B).
- Bath solution (B) has a pH not lower than 1.0.
- the bath solution (B) has a pH of less than 2.5, and more preferably less than 1.8.
- the preferred pH range of bath solution (B) is thus 1.0 to ⁇ 1.8.
- the main component of bath solution (B) is water.
- the desired pH of the bath solution (B) can be adjusted with the aid of acids, in particular a mixture of sulfuric acid and hydrofluoric acid.
- this mixture may comprise at least 0.5% by weight, particularly preferably at least 1% by weight, of sulfuric acid and 1 to 200 ppm, preferably 5 to 50 ppm of hydrofluoric acid.
- the bath solution (B) of the reaction bowl (2) preferably contains a free acid content in points of at least 3, more preferably of at least 10, but preferably of not more than 30.
- the reaction rinse (2) additionally contains iron ions in an amount of at least 0.1 g / kg, in particular at least 1 g / kg, but preferably not more than 10 g / kg, more preferably not more than 6 g / kg in each case based on the bath solution (B).
- the bath solution (B) further comprises a total of at least 0.02 g / kg of water-soluble compounds of the elements zirconium and / or titanium in each case based on the respective elements.
- the reaction rinse (2) comprises a total of less than 1 g / kg, preferably less than 0.6 g / kg, more preferably less than 0.3 g / kg, but preferably at least 0.1 g / kg, more preferably at least 0.2 g / kg of water-soluble compounds of the elements zirconium and / or titanium in each case based on the respective elements.
- the water-soluble compounds may be any of the water-soluble compounds of these metals known in the art and suitable for this purpose.
- compounds are "water-soluble" if their solubility in deionized water having a conductivity of not more than 1 ⁇ 8 ⁇ ⁇ 1 at a temperature of 20 ° C. is at least 1 g / l.
- the water-soluble titanium compounds which can be used according to the invention include in particular salts and esters of titanic acid, the so-called titanates.
- titanates for example, hUTiC and the corresponding alkoxides such as tetraethyl titanate can be used for this purpose.
- titanium (IV) and titanium (l l l) halides such as TiC and TiCU can be used.
- the hexafluoroacids of the titan H2T1F6 and their water-soluble salts can be used, such as (NhU ⁇ TiFe, Li2TiF6, K2T1F6 and Na2TiF6.
- (NH4) 2Zr (C03) 2 (OH) 2, zirconium acetates, zirconium halides such as ZrCu and hexafluorozirconic acid and their salts such as (NH4) 2ZrF6, Li2ZrF6, 2ZrF6 and Na2ZrF6 can be used.
- F ZrFe and its water-soluble salts are suitable.
- the bath solution (B) it is generally preferred for rapid conversion of the metal surfaces of the components that the bath solution (B) have a minimum level of free fluoride of 5 ppm.
- the bath solution (B) has an aluminum content of less than 5 g / l. Should this value be reached or exceeded, it may be necessary to lower the aluminum content, for example by partial or complete replacement of the bath solution.
- the "bringing into contact” of the components with the respective bath solutions in the method according to the invention comprises any such time-limited technical measure on the basis of which the components are wetted with the respective bath solution Coating with the respective bath solution, but are not limited to these possibilities.
- the bringing into contact of the plurality of iron or aluminum components with the bath solutions in the pickling (1) and / or the reaction rinse (2) can be carried out over a period of 0.01 min to 10 min, preferably 0.05 min to 5 minutes, more preferably from 0.25 minutes to 3 minutes.
- contacting may occur at an elevated temperature of the respective bath solution (s).
- the contacting is carried out at elevated temperature of the bath solutions (A) and (B).
- the contacting is carried out at a temperature of from 5 ° C to 90 ° C, preferably from 10 ° C to 65 ° C, more preferably from 15 ° C to 40 ° C, and most preferably at 20 ° C up to 30 ° C performed.
- the stain (1) and the reaction bowl (2) it is possible for the stain (1) and the reaction bowl (2) to be carried out at different temperatures for different lengths of time depending on the respective component, such as composition and size of the surface, and the bath solutions (A) and (B) ,
- the aluminum components pass through the same reaction bowl (2)
- the method according to the invention may comprise further steps.
- the plurality of iron components after the reaction column (2) undergo a wet chemical conversion layer formation, for example on the basis of the same water-soluble compounds as used in the reaction column (2), but at a pH in the range of 2.5. 4,0, or based on a phosphating.
- the plurality of iron components after the reaction rinse (2) preferably undergo activation (3) followed by phosphating (4).
- the phosphating (4) is preferably a zinc phosphating.
- Activation (3), phosphating (4) and zinc phosphating are well established in the art and can be carried out by known methods and chemicals.
- Activation (3) increases the number of phosphate crystals growing per unit of metal surface during phosphating. Furthermore, the sizes of the single crystals in the final phosphate layer are in some cases considerably reduced, the basis weight of the phosphate layer is reduced, and the time required to cover the metal surface with phosphate crystals is shortened.
- the activation additionally fixes crystal nuclei on the metal surface, which serve as phosphate nucleation points.
- the activation may be carried out by any methods and chemicals known in the art and suitable for this purpose.
- the iron component may be treated with a dispersion of titanium phosphate, tertiary zinc phosphate and / or tertiary iron (II) zinc phosphate.
- the phosphating (4) can be carried out with the aid of a phosphate-containing solution.
- the provision of the phosphate-containing solution can be carried out by adding, for example, phosphoric acid and / or salts of phosphoric acid, such as NasPC, K3PO4, Ca3 (PO4) 2 or mixtures thereof to water or an aqueous solution.
- the phosphating (4) is a zinc phosphating
- the phosphate-containing solution further contains zinc ions.
- other known in the art agents such as accelerators and heavy metal cations selected from manganese, copper, nickel and / or cobalt ions can be added.
- the aluminum parts after the reaction rinse (2) do not undergo the phosphating (4), preferably neither the activation (3) nor the phosphating (4), particularly preferably no phosphating, and in particular preferably no further wet-chemical pretreatment but preferably at least one, preferably two rinse steps.
- a "rinsing step”, as used in the context of the invention, is not a wet chemical treatment step and serves solely to completely or partially remove water soluble residues, particles and kneading components adhered to the component from a previous wet chemical treatment step, without the component to be treated
- active components are understood to mean exclusively components which have a significant surface coverage of the components with metallic or semi-metallic foreign elements, ie elements whose surface portion in the contact region of the component with the the active component contained liquid immediately before contacting less than 5 at .-% measured by X-ray photoelectron spectroscopy is (Al- ⁇ radiation and 54.7 ° angle between S trap incidence and detector), or cause organic compounds and thereby consume.
- a significant surface coverage is in any case when the proportion of metallic or semi-metallic foreign elements on the surfaces of the component immediately after the treatment step is on average greater than 1 mg / m 2 based on the foreign element.
- the aluminum and iron components before the reaction rinse (2) undergo an alkaline degreasing and cleaning.
- the aluminum and iron components preferably undergo the same alkaline degreasing and cleaning, whereby the iron components always undergo said degreasing and cleaning before the stain (1).
- This alkaline degreasing and cleaning can be carried out using any degreasing and cleaning method known in the art and suitable for this purpose. These include, but are not limited to, the treatment with solutions containing agents selected from the group of surfactant-active substances and soaps Group are limited. Alternatively, organic solvents, such as. As alcohols, are used for degreasing and cleaning.
- a plurality of magnesium components are treated in series, wherein each of the magnesium components also the same reaction rinse (2) as the iron and aluminum components passes through, but without having a stain (1) to go through.
- Magnetic components have substantially surfaces of magnesium and / or magnesium alloys, preferably more than 60%, more preferably more than 80%, most preferably more than 90% of all metallic surfaces of the magnesium components surfaces of magnesium and / or its alloys.
- all metallic surfaces of the magnesium components are surfaces of magnesium and / or its alloys.
- the bath solution (B) of the reaction bowl (2) may be advantageous for the bath solution (B) of the reaction bowl (2) to have a slightly higher pH than the values indicated above as preferred, for example in the range from 2 to 2.5.
- the period and temperature of the reaction bowl (2), as indicated above for the iron and aluminum components, are transferable to the magnesium components which are subjected to the reaction bowl (2).
- a method is preferred in which the same undergo no further wet chemical pretreatment, which is a phosphating, preferably no further wet chemical pretreatment, but preferably at least one, more preferably at least two rinsing steps.
- a rinsing step in the context of the present invention is not a wet-chemical treatment step and serves solely to completely or even partially remove the agent with which the component has previously been treated.
- Such rinsing steps are known in principle in the prior art.
- the rinsing step can be adapted to the rinsing step performed before and after. Thus, for example, such a rinsing step with water without additives optionally be carried out at elevated temperature.
- Water but also additives, such as acids, alkalis, washing-active substances or soaps are added. Further, the components may also be cleaned by means of organic solvents such as alcohols or organic solvent mixtures.
- the rinsing step may be accomplished by contacting as defined herein.
Abstract
Applications Claiming Priority (2)
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DE102014225237.7A DE102014225237B3 (de) | 2014-12-09 | 2014-12-09 | Verfahren zur nasschemischen Vorbehandlung einer Vielzahl von Eisen- und Aluminiumbauteilen in Serie |
PCT/EP2015/078466 WO2016091703A1 (fr) | 2014-12-09 | 2015-12-03 | Réception de métaux légers dans un procédé de prétraitement et de décapage de l'acier |
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EP3230491A1 true EP3230491A1 (fr) | 2017-10-18 |
EP3230491B1 EP3230491B1 (fr) | 2019-02-20 |
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EP15804762.1A Active EP3230491B1 (fr) | 2014-12-09 | 2015-12-03 | Réception de métaux légers dans un procédé de prétraitement et de décapage de l'acier |
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EP (1) | EP3230491B1 (fr) |
DE (1) | DE102014225237B3 (fr) |
ES (1) | ES2718759T3 (fr) |
WO (1) | WO2016091703A1 (fr) |
Cited By (1)
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US11408078B2 (en) * | 2017-12-20 | 2022-08-09 | Henkel Ag & Co. Kgaa | Method for the anti-corrosion and cleaning pretreatment of metal components |
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EP3569743A1 (fr) * | 2018-05-16 | 2019-11-20 | Henkel AG & Co. KGaA | Nettoyage de charriot dans un cycle d'opération de laquage par électro-immersion |
CN108823578A (zh) * | 2018-06-19 | 2018-11-16 | 张家港保税区恒隆钢管有限公司 | 一种无缝钢管毛管酸洗工艺 |
EP4223906A1 (fr) * | 2022-02-02 | 2023-08-09 | Henkel AG & Co. KGaA | Séquence de procédé pour le dérochage et la passivation d'acier |
Family Cites Families (7)
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DE2031358C3 (de) * | 1970-06-25 | 1981-10-15 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels saurer, komplexe Fluoride enthaltender, Lösungen |
US4391652A (en) * | 1982-01-29 | 1983-07-05 | Chemical Systems, Inc. | Surface treatment for aluminum and aluminum alloys |
DE4317217A1 (de) * | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chromfreie Konversionsbehandlung von Aluminium |
DE19921842A1 (de) * | 1999-05-11 | 2000-11-16 | Metallgesellschaft Ag | Vorbehandlung von Aluminiumoberflächen durch chromfreie Lösungen |
JP4205939B2 (ja) * | 2002-12-13 | 2009-01-07 | 日本パーカライジング株式会社 | 金属の表面処理方法 |
WO2008100476A1 (fr) * | 2007-02-12 | 2008-08-21 | Henkel Ag & Co. Kgaa | Procédé de traitement de surfaces métalliques |
DE102008038653A1 (de) * | 2008-08-12 | 2010-03-25 | Henkel Ag & Co. Kgaa | Sukzessive korrosionsschützende Vorbehandlung von Metalloberflächen in einem Mehrstufenprozess |
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2014
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2015
- 2015-12-03 WO PCT/EP2015/078466 patent/WO2016091703A1/fr active Application Filing
- 2015-12-03 EP EP15804762.1A patent/EP3230491B1/fr active Active
- 2015-12-03 ES ES15804762T patent/ES2718759T3/es active Active
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US11408078B2 (en) * | 2017-12-20 | 2022-08-09 | Henkel Ag & Co. Kgaa | Method for the anti-corrosion and cleaning pretreatment of metal components |
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WO2016091703A1 (fr) | 2016-06-16 |
DE102014225237B3 (de) | 2016-04-28 |
ES2718759T3 (es) | 2019-07-04 |
EP3230491B1 (fr) | 2019-02-20 |
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