EP2013372A1 - Method for the production and removal of a temporary protective layer for a cathodic coating - Google Patents
Method for the production and removal of a temporary protective layer for a cathodic coatingInfo
- Publication number
- EP2013372A1 EP2013372A1 EP08707416A EP08707416A EP2013372A1 EP 2013372 A1 EP2013372 A1 EP 2013372A1 EP 08707416 A EP08707416 A EP 08707416A EP 08707416 A EP08707416 A EP 08707416A EP 2013372 A1 EP2013372 A1 EP 2013372A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- zinc
- protective layer
- dip coating
- cathodic
- 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
- 239000011241 protective layer Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000010410 layer Substances 0.000 claims abstract description 68
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 25
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003618 dip coating Methods 0.000 claims abstract description 14
- 229910000760 Hardened steel Inorganic materials 0.000 claims abstract description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000000155 melt Substances 0.000 abstract 5
- 230000004888 barrier function Effects 0.000 abstract 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 14
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000005422 blasting Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000004210 cathodic protection Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000003670 easy-to-clean Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005270 abrasive blasting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 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 compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/003—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods using material which dissolves or changes phase after the treatment, e.g. ice, CO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/08—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for polishing surfaces, e.g. smoothing a surface by making use of liquid-borne abrasives
- B24C1/086—Descaling; Removing coating films
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
- C21D8/0484—Application of a separating or insulating coating
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
Definitions
- the invention relates to a method for producing and removing a temporary protective layer for a cathodic coating on carrier metals.
- a method for removing a layer of a component is known.
- This is a layer of organic binder that is to be removed from a substrate without damaging the substrate.
- a jet of dry ice particles is guided over the surface, so that material is removed from the layer containing an organic binder by the action of the occurring dry ice particles.
- the removal of dry ice is intended to prevent contamination by foreign substances and to not impair the metallic basic body of the component.
- a method for removing a metal layer wherein a layer system comprising the metal layer and a substrate coated by the metal layer and the removal process is a blasting process.
- the blasting process can be a sandblasting process, wherein the metal layer is strongly cooled in order to achieve a low-temperature embrittlement of the layer relative to the substrate.
- a method and a device for irradiating with different blasting agents are known.
- an abrasive blast treatment with blasting agents in which the abrasive effect of the blasting agent is between the blasting agents present in fluid form under normal conditions and the blasting agents present in solid state under normal conditions.
- a mixture of a first blasting agent such as dry ice and a second abrasive blasting agent such as sand is used.
- DE 199 42 785 Al a method for removing solid processing residues, surface coatings or oxide layers is known, only where a cleaning should take place where fixed processing residues.
- the cleaning can take place here with steam jets, dry ice blasting or cleaning with technically induced shock waves, so-called laser cleaners.
- the CÜ 2 cleaning can be done by known dry ice pellets.
- DE 102 43 035 B4 discloses a method and a device for removing layers which are formed by heating and cooling on metal pieces.
- the solid particles in abrasive pressurized gas jets should not completely remove from metal workpieces the pressurized gas stream with the aid thereof, for example, dry ice particles be applied to the metal workpiece to be cleaned, preheated and have a temperature which is greater than the temperature of the air surrounding the metal workpiece and / or as the surface temperature of the metal workpiece. This is intended to ensure that, on the one hand, the metal workpiece is not excessively overcooled and, on the other hand, that the compressed gas is at least substantially free of moisture and thus undesired formation of condensate is avoided.
- the layers to be removed from the surface of the piece of metal are removed by the mechanical action of the high velocity impacting dry ice particles and by the localized cooling of the surface and the layer due to the dry ice particles.
- This very fine protective layer may for example consist of magnesium oxide or aluminum oxide or mixtures thereof. From WO 2005/021820 it is also known to apply such a method during roll profiling.
- the object of the invention is to provide a method with which the paint adhesion can be improved on provided with a cathodic protective layer hardened steel components.
- the paint adhesion may not be optimal in the case of cathodic anticorrosion coatings provided with a fine surface protection coating.
- there is no alternative to the formation of these thin layers since otherwise only a post-galvanizing of these components could be carried out, which is very complex and expensive.
- the fine protective layer of one or more oxygen-affine elements is formed so that it can be removed again, ie only temporarily present, in order to protect the cathodic layer during heating above the austenitizing temperature, ie. H. of the glow, to ensure.
- this thin protective layer of at least one oxide of the oxygen-containing elements is formed such that cracks and / or defects form in this layer. These cracks allow to detach the scales of the oxide limited by the cracks and / or defects by means of dry ice irradiation.
- the radiation is carried out only with dry ice without additives, wherein the dry ice particles penetrate through the cracks and / or defects in the cavities under the protective layer and sublimate under up to 800-fold volume increase.
- the potentially loose or to be dissolved particles are blasted from the oxide of the / Sauerstoffäffinen elements / element together with any zinc oxide particles thereon.
- the additional thermal shock caused by the deep cold dry ice particles leads to further thermal stresses in the oxide / oxygen-sensitive element / element oxide layer and thus promotes the desired removal.
- an abrasive removal should and must be avoided, as this attacks the cathodic protective layer.
- the desired zinc or zinc-iron layer required for the cathodic corrosion protection is not influenced by this nor is it removed. With the method according to the invention thus a selective removal of poorly adhering oxides is possible. Good adhering oxides on the surface, on the other hand, remain on the surface and have no negative effect on the lability.
- the thickness and the crackiness of the fine protective layer of the oxide of the / the oxygen element / element arrives at the pretreatment of the bare steel strip and its influence on the interfacial kinetics or formation between zinc and steel substrate in the hot dip coating and on the zinc deposit.
- Pretreatment is to be understood as meaning a pre-oxidation of the bare steel strip, as described in DE 100 59 566 B3 and in EU Research Report No. 7210-PA / 118.
- This type of treatment is common to the property profile of To optimize steels with high strength. This improves the adhesion properties of the zinc coating in hot dip coating, in particular in steel strips with high alloy constituents.
- An inhibiting layer is a layer which occurs as a result of aluminum addition in the zinc bath between the steel substrate and the zinc layer during the continuous hot-dip coating and, if appropriate, subsequent heat treatment.
- the object of the inhibition layer in general is to brake an excessively strong alloy or reaction between iron and zinc.
- this inhibitor layer is made too thick, the reaction of zinc with iron during heating over austenitizing temperature slows down and the overlying and further slightly increasing layer of the oxide of the oxygen-containing element (s) becomes of the resulting iron-zinc phases little or no damage.
- the thickness of the fine protective layer grows only slowly and there is also no severe cracking, since the now rather thin Al 2 ⁇ 3 layer lays like a thin skin over the iron-zinc phases. The same effect occurs when the zinc coating is too high.
- Figure 1 a layer structure according to the invention, which is easy to work with the inventive method
- FIG. 2 a comparative illustration of a surface that is not easy to clean
- FIG. 3 shows a surface to be cleaned according to FIG. 1 in a scanning electron microscope top view
- FIG. 4 shows a plan view of a surface which is difficult to clean according to FIG. 2 in a scanning electron micrograph
- FIG. 5 shows the surface of the sample according to FIG. 3 after the cleaning step according to the invention
- FIG. 6 shows a surface according to FIG. 4 after carrying out a cleaning process
- FIG. 7 shows schematically the cleaning process according to the invention
- the surface shown in FIG. 1, in which cracks and / or defects due to the heat treatment or hardening occur in the Al 2 O 3 protective layer, is ideally to be cleaned with dry ice.
- the dry ice particles penetrate through the cracks shown into the cavities under the Al 2 O 3 layer and sublimate there as already explained.
- the dry ice cleaning is carried out such that the dry ice particles do not attack the iron under the Al 2 ⁇ 3 layer and do not even break off the particles that adhere so firmly to the iron-zinc layer that they for the Liability is no problem.
- the necessary requirements are met, according to which cavities must be present under the Al 2 ⁇ 3 layer, the Al 2 O 3 - layer must have a certain thickness and also cracks must be present.
- the cracks also allow molten zinc to evaporate, reacting with the atmospheric oxygen to form zinc oxide and recondensing on the Al 2 O 3 protective layer.
- FIG. 2 it can be seen that both the wavy The thickness of the iron-zinc layer is lower and the Al 2 O 3 layer has larger closed areas that go beyond the cavities caused by the waviness of the iron-zinc layer. Accordingly, little zinc oxide is formed in the region of the cracks. Since parts of the cavities are covered by the Al 2 O 3 layer, it is not possible to cause blistering by sublimation in the cavities.
- FIGS. 3 and 4 the states illustrated diagrammatically in FIGS. 1 and 2 are shown in a plan view by means of an electron microscope. In both cases, it is a sheet of 1.0 mm thick, which was annealed at 910 0 C for 250 sec. In a radiant furnace and was then cured between cooled steel plates.
- FIG. 4 shows the surface after curing in the case of a thick inhibiting layer formation and / or an excessively high zinc deposit. Since the AI 2 O 3 protective layer is comparatively thin in this case, the electron beam can penetrate it more easily. The cavities of the Al 2 ⁇ 3 protective layer located are therefore seen in the receptacle as dark areas, since fewer back-scattered electrons from the Al 2 O 3 protective layer contributes to the detector signal.
- the thickness of the Al 2 O 3 layer is about 150 nm to 200 nm.
- the state shown in FIG. 3 is the desired state, while the undesirable state shown in FIG. 4 corresponds to the conditions of FIG ,
- FIG. 5 shows a surface according to FIG. 3 which has been subjected to the cleaning method according to the invention.
- the iron-zinc phases are very evident.
- a big Al 2 O 3 - and zinc oxide occupancy is no longer recognizable.
- This surface produced according to the invention can be very well phosphated or post-treated in some other way and shows a very good paint adhesion.
- FIG. 6 shows the surface according to FIG. 4 after the dry ice cleaning process has been carried out.
- the darker areas show uncoated Al 2 O 3 and a surface that only allows poor paintability.
- the pretreatment and hot dip coating is carried out in such a way that a FeO layer greater than 100 nm but less than 1000 nm is formed during the preoxidation and preferably forms an inhibiting layer which has an aluminum content of 0.15 g / m 2 to 0, 4 g / m 2 has.
- an increased zinc-iron reaction occurs, which leads to the breaking up of the Al 2 O 3 protective layer.
- Higher aluminum contents lead to a state as described in FIG.
- Lower aluminum contents lead to incomplete formation of the inhibiting layer and to a zinc-iron reaction already during the galvanizing process. This in turn means that the zinc can chip off during cold forming.
- the zinc layer support for carrying out the method according to the invention preferably lies between Z100 and Z200, which means between 7 ⁇ m and 14 ⁇ m per side.
- the through-reaction of the zinc-iron phases can be delayed to the surface, whereby the Al 2 O 3 -Schilli is only slightly damaged and thus remains thin.
- cathodic protection may be too low.
- a sheet of 22MnB5 steel 1.0mm thick is subjected to pre-oxidation and hot dip coating of about 0.2% by weight aluminum in the zinc bath.
- the pre-oxidation is carried out so that a FeO layer thickness of greater than 100 nm but less than 1,000 nm is set.
- the galvanizing is carried out in such a way that a zinc coating Z200, that means 14 ⁇ m per side is achieved.
- the aluminum content of the inhibiting layer is adjusted to 0.3 g / m 2 .
- the sheet is then placed in a 910 ° C hot air oven with normal air atmosphere for four minutes. As a result, a layer formation according to FIGS. 3 and 5 or according to FIG. 1 can be seen. This layer is easy to clean with dry ice and The result is the surface according to Figure 5 and in subsequent experiments, the correspondingly good paint adhesion.
- a sheet of 22MnB5 steel 1.0mm thick is subjected to a preoxidation and a hot dip coating of about 0.2% by weight aluminum in the zinc bath.
- the pre-oxidation of the bare steel sheet is carried out so that a FeO layer thickness of greater than 100 nm and less than 1,000 nm is set.
- the zinc coating is carried out in such a way that a zinc coating of Z200, ie 14 ⁇ m per side, is achieved.
- the aluminum content of the inhibitor layer is set to 0.8 g / m 2 and the annealing conditions are as in Example 1.
- an aluminum oxide-rich surface is achieved with little zinc oxide, which is difficult to clean with dry ice.
- the surface corresponds to Figure 6 or before cleaning Figure 4 and in subsequent Lackier barnen results in the poor paint adhesion due to large-area Al 2 O 3 occupancy.
- a steel sheet according to Examples 1 and 2 is formed instead of a zinc coating Z200 with a zinc coating Z300, ie 21 microns per side.
- the pre-oxidation of the bare steel strip is carried out so that a FeO layer thickness of greater than 100 nm and less than 1,000 nm is set.
- the aluminum content of the inhibiting layer is adjusted to 0.3 g / m 2 .
- the sheet is then placed in a 910 ° C hot air oven with normal air atmosphere for four minutes. Again, the not inventive Al 2 ⁇ 3 ⁇ rich surface with little zinc oxide forms again, which is poorly cleansed with dry ice and the illustrated Surface corresponds in Figure 4. In subsequent Lackier barnen also a poor paint adhesion is achieved.
- the cathodic protective layer protects the steel against oxidation during the heating process and in particular scale formation protects and wherein after a heat treatment and hardening of the steel component with simple means a very good paintable surface is created.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007022174A DE102007022174B3 (en) | 2007-05-11 | 2007-05-11 | Method for creating and removing a temporary protective layer for a cathodic coating |
PCT/EP2008/000721 WO2008138412A1 (en) | 2007-05-11 | 2008-01-30 | Method for the production and removal of a temporary protective layer for a cathodic coating |
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EP2013372A1 true EP2013372A1 (en) | 2009-01-14 |
EP2013372B1 EP2013372B1 (en) | 2012-03-14 |
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EP08707416A Active EP2013372B1 (en) | 2007-05-11 | 2008-01-30 | Method for the production and removal of a temporary protective layer for a cathodic coating |
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US (1) | US9822436B2 (en) |
EP (1) | EP2013372B1 (en) |
JP (1) | JP5226067B2 (en) |
KR (1) | KR101448188B1 (en) |
CN (1) | CN101707942B (en) |
AT (1) | ATE549429T1 (en) |
DE (1) | DE102007022174B3 (en) |
ES (1) | ES2382496T3 (en) |
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DE102007061489A1 (en) * | 2007-12-20 | 2009-06-25 | Voestalpine Stahl Gmbh | Process for producing hardened hardenable steel components and hardenable steel strip therefor |
DE102009015160A1 (en) | 2009-03-26 | 2010-09-30 | Bayerische Motoren Werke Aktiengesellschaft | Process for producing a coated and / or available sheet metal part with a corrosion protection coating |
DE102009016852A1 (en) | 2009-04-08 | 2010-10-14 | Bayerische Motoren Werke Aktiengesellschaft | Process for the preparation of heat-treated sheet metal parts from a steel sheet material with a corrosion protection coating and such sheet metal part |
WO2011101158A1 (en) * | 2010-02-19 | 2011-08-25 | Tata Steel Nederland Technology Bv | Strip, sheet or blank suitable for hot forming and process for the production thereof |
IT1399945B1 (en) * | 2010-04-29 | 2013-05-09 | Turbocoating S P A | METHOD AND APPARATUS FOR REMOVING CERAMIC COATINGS, WITH CARBON DIOXIDE SOLID SOLID. |
DE102010037077B4 (en) * | 2010-08-19 | 2014-03-13 | Voestalpine Stahl Gmbh | Process for conditioning the surface of hardened corrosion-protected steel sheet components |
EP2474649A1 (en) * | 2011-01-05 | 2012-07-11 | Voestalpine Stahl GmbH | Method for treating the surface of a substrate with a protective coating |
CN102380491A (en) * | 2011-08-01 | 2012-03-21 | 迪普干冰制造(大连)有限公司 | Heating dust suction and dry ice cleaning surface depainting treatment equipment and method |
WO2013160566A1 (en) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Method for producing a metal sheet having oiled zn-al-mg coatings, and corresponding metal sheet |
JP5963271B2 (en) * | 2013-09-03 | 2016-08-03 | 昭和電工ガスプロダクツ株式会社 | Metal processing method |
JP6509483B2 (en) * | 2013-09-03 | 2019-05-08 | 昭和電工ガスプロダクツ株式会社 | Melting equipment |
US10619223B2 (en) | 2016-04-28 | 2020-04-14 | GM Global Technology Operations LLC | Zinc-coated hot formed steel component with tailored property |
US10385415B2 (en) | 2016-04-28 | 2019-08-20 | GM Global Technology Operations LLC | Zinc-coated hot formed high strength steel part with through-thickness gradient microstructure |
KR102445264B1 (en) * | 2016-08-09 | 2022-09-21 | 신토고교 가부시키가이샤 | How to remove attachments |
JP6751530B2 (en) * | 2017-03-17 | 2020-09-09 | 新東工業株式会社 | How to remove deposits |
JP6751529B2 (en) * | 2016-08-09 | 2020-09-09 | 新東工業株式会社 | How to remove deposits |
US11613789B2 (en) | 2018-05-24 | 2023-03-28 | GM Global Technology Operations LLC | Method for improving both strength and ductility of a press-hardening steel |
CN112534078A (en) | 2018-06-19 | 2021-03-19 | 通用汽车环球科技运作有限责任公司 | Low density press hardened steel with enhanced mechanical properties |
CN109551372A (en) * | 2018-11-07 | 2019-04-02 | 广州供电局有限公司 | The restorative procedure of substation's internal corrosion steel construction piece |
US11530469B2 (en) | 2019-07-02 | 2022-12-20 | GM Global Technology Operations LLC | Press hardened steel with surface layered homogenous oxide after hot forming |
EP3872230A1 (en) | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Method for producing hardened steel components with a conditioned zinc alloy corrosion protection layer |
EP3872229A1 (en) * | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Method for producing hardened steel components with a conditioned zinc alloy corrosion protection layer |
EP3872231A1 (en) | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Method for conditioning the surface of a metal strip coated with a zinc alloy corrosion protection layer |
DE102022116082A1 (en) | 2022-06-28 | 2023-12-28 | Voestalpine Metal Forming Gmbh | Process for conditioning the surfaces of heat-treated galvanized steel sheets |
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DE19942785A1 (en) * | 1999-09-08 | 2001-03-22 | Thyssen Krupp Automotive Ag | Processing residue, surface coating or oxide layer removal process, |
EP1321625B1 (en) * | 2001-12-21 | 2004-09-22 | Siemens Aktiengesellschaft | Method for removing a metallic layer |
DE10243035B4 (en) * | 2002-09-17 | 2006-01-05 | Daimlerchrysler Ag | Method and device for removing layers formed by heating and cooling on metal workpieces |
BRPI0412599B1 (en) | 2003-07-29 | 2016-05-17 | Voestalpine Automotive Gmbh | method for producing hardened structural parts made of sheet steel plate. |
EP1561542A1 (en) * | 2004-02-03 | 2005-08-10 | Siemens Aktiengesellschaft | Process of removing of component layer |
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KR101448188B1 (en) | 2014-10-07 |
ES2382496T3 (en) | 2012-06-08 |
JP5226067B2 (en) | 2013-07-03 |
EP2013372B1 (en) | 2012-03-14 |
US9822436B2 (en) | 2017-11-21 |
KR20100017770A (en) | 2010-02-16 |
JP2010526937A (en) | 2010-08-05 |
DE102007022174B3 (en) | 2008-09-18 |
US20110139308A1 (en) | 2011-06-16 |
ATE549429T1 (en) | 2012-03-15 |
WO2008138412A1 (en) | 2008-11-20 |
CN101707942B (en) | 2012-08-22 |
CN101707942A (en) | 2010-05-12 |
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