EP2195471A1 - Anti-corrosion coating with improved adhesion - Google Patents
Anti-corrosion coating with improved adhesionInfo
- Publication number
- EP2195471A1 EP2195471A1 EP08802862A EP08802862A EP2195471A1 EP 2195471 A1 EP2195471 A1 EP 2195471A1 EP 08802862 A EP08802862 A EP 08802862A EP 08802862 A EP08802862 A EP 08802862A EP 2195471 A1 EP2195471 A1 EP 2195471A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- coating
- sheet
- magnesium
- hot
- 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.)
- Withdrawn
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 238000005260 corrosion Methods 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 59
- 239000011701 zinc Substances 0.000 claims abstract description 59
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 47
- 239000011777 magnesium Substances 0.000 claims abstract description 47
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 38
- 239000010959 steel Substances 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract 3
- 238000010791 quenching Methods 0.000 claims abstract 3
- 230000007797 corrosion Effects 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 69
- 229940091250 magnesium supplement Drugs 0.000 description 45
- 239000003973 paint Substances 0.000 description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000000137 annealing Methods 0.000 description 9
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005246 galvanizing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical class CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229920005027 Ultraform® Polymers 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 zinc-aluminum-magnesium Chemical compound 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical group [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000725 suspension Substances 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
-
- 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
-
- 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
- C23C2/29—Cooling or quenching
Definitions
- the invention relates to a corrosion protection coating with improved paint adhesion.
- This very fine protective layer may, for example, consist of aluminum oxide.
- Investigations have shown that in the main oxygen-type element used, namely aluminum in the zinc coating, an aluminum oxide layer forms on the surface, which is very hard, vitreous and smooth and which apparently hampers good paint adhesion. If you paint such hardened hot-dip galvanized sheets, the paint adheres poorly to the sheet. Possibly the paint dissolves together with aluminum oxide layer or the paint binds badly on the alumina. One way to improve paint adhesion is therefore to previously remove the poorly adherent oxide film.
- DE 697 30 212 T2 discloses a hot-dip coated steel sheet with excellent corrosion properties and a process for its production which has a zinc-aluminum-magnesium coating, the coating containing, in addition to zinc, 4-10% by weight of aluminum and 1 - 4 wt .-% magnesium.
- a zinc coating and a method of applying it to sheet steel are known, whereby the zinc coating may contain 3-5% by weight of aluminum and 1 to 4% by weight of magnesium. This coating should also provide good corrosion resistance.
- WO 2006 002 843 A1 discloses a steel sheet with a hot dip coating based on zinc, this hot dip coating additionally comprising 0.3 to 2.3% by weight of magnesium and 0.6 to 2.3% by weight of aluminum may contain.
- US Pat. No. 6,379,820 B1 likewise discloses a hot-dip coated steel sheet, the coating metal or the coating comprising a zinc-aluminum-magnesium coating with 4-10% by weight of aluminum and 1-4% by weight. Magnesium is.
- the composition of the coating should have an influence especially on crystalline aluminum phases in the metal.
- a coated steel sheet is also known, which is coated with a zinc alloy.
- Said zinc alloy may contain 0.5-5% by weight of aluminum and 0.01-2% by weight of magnesium and additionally lead.
- a steel strip coated in this way is to be subjected to a diffusion process after the coating in order to enrich the iron content in the layer.
- the object of the invention is to provide a corrosion protection coating which, on the one hand, provides reliable protection against oxidation and evaporation of the zinc layer during curing and, secondly, enables good paint adhesion without post-processing of the corrosion protection layer.
- Another object of the invention is to provide a method for producing a hardened sheet metal component with a corrosion protection coating with improved adhesion. This object is achieved by a method having the features of claim 3. Advantageous developments are characterized in the dependent claims.
- Another object of the invention is to provide a hardened sheet metal component having a corrosion protection coating with improved adhesion.
- inventively coated sheets can be heated more quickly to temperatures of about 900 0 C, as hot-dip galvanized sheets without magnesium supplement.
- the coating of a steel sheet is formed by providing the steel sheet in a conventional dip-dip coating process with a metal coating containing 0.1 to 5% aluminum and 0.2 to 2% magnesium, balance zinc.
- a metal coating containing 0.1 to 5% aluminum and 0.2 to 2% magnesium, balance zinc.
- the explanation for the good adhesion of the oxide layer is the following:
- the magnesium is in the group of network converters. It forms crystalline oxides and, moreover, has a greater tendency than aluminum to form oxides. As a result, the aluminum is no longer possible when heated to 900 0 C to form a covering glassy network of alumina.
- a solid-state reaction forms well-adhering oxide. It may also be possible to form a compound MgAl 2 O 4 , the spinel with zinc oxide.
- FIG. 1 shows a diagram of the surface of hardened hot-dip-galvanized sheet metal according to the invention with magnesium in the layer;
- FIG. 2 a scanning electron micrograph of the
- Figure 3 is a schematic of the surface of a prior art hot dip dip galvanized sheet having a poorly adherent oxide layer
- FIG. 4 shows a scanning electron micrograph of the surface of the annealed sheet according to FIG. 3;
- Figure 5 the appearance of the heated and heated to 900 0 C sheets with a sheet coated according to the invention (left), and a sheet metal according to the prior art (right);
- Figure 6 the paint adhesion to a annealed according to the invention coated sheet (left) and a sheet metal according to the prior art (right) after corrosive removal;
- FIG. 7 is a photomicrograph of the cross-section of annealed sheet of the prior art
- FIG. 8 shows a cross section of the annealed sheet coated in accordance with the invention
- FIG. 9 GDOES analysis of the hot-dip galvanized and non-heat treated sheet according to the invention.
- Figure 10 GDOES analysis of the hot-dip galvanized and non-heat treated sheet of the prior art
- Figure 11 GDOES analysis of the inventively coated and heated to 900 0 C sheet
- Figure 12 GDOES analysis of the heated to 900 0 C and cured sheet according to the prior art
- FIG. 13 technical data of the trial painting of the sample sheets
- FIG. 14 arrangement of the bonding of sample strips
- FIG. 15 tensile shear strengths of the hardened sheet according to the invention and a comparison sheet according to the prior art
- FIG. 16 shows the emissivity of a steel sheet coated in accordance with the invention during annealing in the radiation furnace, which is only 895.degree.
- FIG. 17 chemical composition of the steel 592519 used for the samples
- FIG. 18 chemical composition of a further test steel 600354
- FIG. 19 the scanning electron micrograph of the
- FIG. 20 a table describing the test results relating to the weldability of sheets according to the invention.
- a coating is used for the anticorrosion coating 1 of a steel sheet 2, which consists essentially of zinc and in addition to zinc contains aluminum in contents of 0.1 to 5% and magnesium in contents of 0.2 to 2%.
- the ratio of aluminum to magnesium can be freely adjusted, with all possible mixtures a success can be achieved.
- FIGS. 1 and 2 The result of the annealing treatment can be seen in FIGS. 1 and 2.
- an oxide layer 4 is present at the top, which follows the wavy or rough structure of the iron-zinc layer 3 on the surface. In the region of the depressions 5 of the roughness, cracks 6 are recognized in the iron-zinc layer 3.
- Figure 2 can be seen very well the rugged surface of a coated according to the invention and then annealed sheet.
- a well-adherent oxide layer has formed during annealing, which may be several microns thick depending on the annealing conditions. It is believed that magnesium, as a network transducer, forms crystalline oxides and has a greater tendency to form oxides than aluminum. As a result, the aluminum is no longer possible when heated to 900 0 C or above. lent to forming a covering, glassy alumina network. A solid-state reaction between the iron-zinc layer and the oxide layer forms the well-adhering oxide, it being assumed that spinels may also be formed with the zinc oxide.
- hot-dip galvanized sheets magnesium addition to the zinc bath of 1.1% by mass
- conventionally hot dip-galvanized sheets without magnesium addition to the zinc bath were analyzed by glow discharge spectroscopy before and after hardening.
- the oxide layer of the heated and cured sheet according to the invention is thicker and is completely removed only after about 50 s. Compared to the thinner oxide layer of the non-inventive sheet, the aluminum signal is present on the surface. while zinc and magnesium are clearly embedded in the oxide layer.
- the aluminum according to the invention could not form a covering aluminum oxide layer during the heating, but it also oxidized magnesium and zinc. This oxide layer adheres very well to the substrate.
- FIG. 7 shows the transverse section of the hardened conventionally hot-dip-galvanized sheet.
- the Zn-Fe layer is about
- the oxide layer is in
- Cross section not visible and consists of an approximately
- FIG. 8 shows the transverse section of the hardened sheet according to the invention.
- the Zn-Fe layer is again about 25 microns thick and has again a structure of bright, zinc-rich phase and zinc-containing ⁇ -Fe mixed crystals. In the zinc-rich areas containing magnesium and aluminum, some are pores.
- the dark surface of the cured sheet according to the invention is an oxide layer up to 4 ⁇ m thick.
- FIGS. 7 and 8 show that even with a coating according to the invention, although it obviously reacts differently or gives a different cover layer, a substantially identical phase composition of the zinc-iron oxide is obtained. Produces phases on the surface of the steel sheet, which is important for a cathodic corrosion protection.
- Applicant's hot-dip galvanizing simulator has zinc-plated phs-ultraform plates of 592519 steel with an alloy containing about 0.2% aluminum and 1.1% magnesium in addition to zinc. The result was a sheet steel coated on both sides 592519 ZMg 190, hereinafter referred to as sheet A.
- Blanks of the size 100 mm ⁇ 100 mm of the two 1.5 mm sheets A and B were annealed in a 910 ° C. hot radiation oven for 5 minutes and then cooled between steel plates and thus hardened.
- Figure 5 shows the two annealed sheets, left the hot-dip galvanized sheet A with magnesium added, the brighter conventional hot dip-galvanized sheet B.
- the two panels A and B were phosphated and KT-painted as in the car manufacturer.
- FIG. 13 shows the process for coating metal sheets by means of automotive phosphating and KT painting by the applicant. Of the Painting process is similar to the process of painting bodies with car manufacturers.
- the insufficient paint adhesion of the samples is due to the formation of the poorly adhering aluminum oxide layer.
- the parting line paint-sheet is the oxide layer.
- the aluminum oxide on hardened, hot-dip-galvanized blanks is not removed during phosphating. There are wide areas without phosphate coating.
- the paint adhesion before corrosion aging of the sheet B was rated on a scale of 0 to 5 with 3.
- the value 0 would not mean a lacquer finish after cross-hatching, a value of 3 means that even large areas within the cross-hatch showed a poor lacquer adhesion and could be removed with adhesive tape.
- Paint adhesion to magnesium-containing hot-dip galvanized samples, i. the sheets A, is very good.
- the paint adhesion before corrosion aging of the sheet A was rated 0 on a scale of 0 to 5, i. no paint was peeled off with the adhesive tape.
- Sheet A the sheet containing magnesium in the zinc layer, shows excellent paint adhesion both in the crosshatch test (rating: 0), at the scribe and also in the area which was bombarded with steel shot.
- Figure 6 shows the samples A and B after the corrosive aging and after the tests (without cross-hatching).
- the adhesive bond was tested by means of a tensile shear test according to DIN EN 1465 with a subsequent assessment of the fracture pattern.
- FIG. 15 shows the tensile shear strength of the adhesive bonds.
- the graph shows the results of the individual experiments, the mean and the standard deviation of the mean for the two variants.
- the tensile shear strength of the adhesive bonds of the hot-dip galvanized sheets by means of magnesium addition to the zinc bath was on average 33 MPa (sheet A) in the cured state.
- the tensile shear strengths of the cured conventional hot-dip galvanized samples were only 14 MPa (plate B).
- a tensile shear strength of 14 MPa is insufficient, especially since the tensile shear strength drops even further after any corrosive stress.
- the reason for the low adhesive adhesion is the poor adhesion of the aluminum oxide to the substrate, which also manifests itself in an adhesive failure of the adhesive bond.
- the tensile shear strength of the sheet with the magnesium-containing zinc coating is close to the adhesive strength itself. Therefore, a cohesive failure was also detectable from the fracture pattern.
- Hot-dip galvanized sheets prepared with a magnesium additive for zinc bath, conventional hot-dip galvanized sheets without addition of magnesium to the zinc bath and electrolytically galvanized sheets without magnesium or aluminum in the zinc coating were heated in a radiation oven to about 900 0 C and then cured.
- the hardened conventionally hot dip galvanized sheets showed the largest weld area and were well weldable.
- the hardened hot dip galvanized sheets with magnesium in the zinc coating showed a wide welding range and could be welded well.
- the hardened electrolytically galvanized sheets could not be welded by resistance spot welding because a very thick zinc oxide layer was formed during annealing.
- the zinc oxide layer therefore formed very thick and dense (several microns thick, very compact) because there was no aluminum and magnesium which could protect the zinc from oxidation.
- the contact resistance of comparable hardened electrolytically galvanized sheets was at an average of about 11.8 milliohms in 10 measurements, ie about twice as high.
- FIG. 20 shows a table which reproduces the results of tests, the coverage of the coating according to the invention being 120 g / m 2 .
- the weldability was assessed at different furnace temperatures and different residence times. It can be seen that, regardless of the furnace temperature, a very good weldability is achieved and the contact resistance of 4.3 m ⁇ on average is well achieved.
- FIG. 16 shows the emissivity of sheet A during annealing in the 895 ° C hot-air furnace.
- the emissivity increases up to a temperature of 700 0 C to ⁇ 0,2 - 0,3 before it steeply increases to a value close to 1 at an annealing temperature close to the oven temperature of 895 ° C.
- the surface after annealing and hardening is black.
- hot-dip galvanized sheets with magnesium in the zinc coating heat up faster because their emissivity at 900 0 C near 1 lies.
- the reason for the low emissivity of conventional hot-dip galvanized sheets at 900 0 C is that the thin aluminum oxide layer is considered to be transparent and the underlying bright zinc-rich phases reflects the heat radiation rather than absorbed.
- hot-dip galvanized sheet metal with magnesium in the zinc coating is heated, dark Zn-Mg-Al oxides are formed, which absorb heat radiation well and thus rapidly heat the sheet. See also Figure 5.
- a 1.5 mm thick steel collar number 600354/2 was galvanized on a hot-dip galvanizing line in a hot-dip galvanizing bath containing magnesium.
- the aluminum content in the zinc bath was about 4%, the magnesium content about 1%.
- the zinc coating was about 14 ⁇ m thick on both sides, i. This was followed by a Zn-Al-Mg suspension of ZnAlMg 200.
- FIG. 19 shows the scanning electron micrograph of the surface of the annealed sheet, which again shows that the oxide layer protrudes into the Zn-Fe phases.
- the paint adhesion before and after corrosion aging was excellent and was judged by cross hatch with 0.
- the sheet showed a high tensile shear strength when glued with Betamate 1496 and was well resistant to welding. At the fair The contact resistance of the sheet was found to be 6.3 m ⁇ with a standard deviation of 2.1 for 10 measurements.
- a corrosion protection layer is achieved which has a very good paint adhesion, a very good bondability and a good weldability compared to a known coating results.
- the addition of magnesium to a defined extent significantly improves a developing oxidation barrier for a zinc-iron layer.
- the emissivity and thus the heatability of a thus coated sheet can be significantly improved.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007048504A DE102007048504B4 (en) | 2007-10-10 | 2007-10-10 | Anti-corrosion coating for steel sheets and method of conditioning a corrosion protection coating |
PCT/EP2008/008594 WO2009049836A1 (en) | 2007-10-10 | 2008-10-10 | Anti-corrosion coating with improved adhesion |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2195471A1 true EP2195471A1 (en) | 2010-06-16 |
Family
ID=39967616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08802862A Withdrawn EP2195471A1 (en) | 2007-10-10 | 2008-10-10 | Anti-corrosion coating with improved adhesion |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2195471A1 (en) |
DE (2) | DE102007048504B4 (en) |
WO (1) | WO2009049836A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009052210B4 (en) * | 2009-11-06 | 2012-08-16 | Voestalpine Automotive Gmbh | Method for producing components with regions of different ductility |
WO2013160568A1 (en) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Method for producing a metal sheet having zn-al-mg coatings, comprising the application of an acid solution, and corresponding metal sheet |
WO2013160569A1 (en) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Method for producing a metal sheet having zn-al-mg coatings, comprising the application of mechanical stress to the coatings, and corresponding metal sheet |
US11613791B2 (en) | 2017-02-21 | 2023-03-28 | Salzgitter Flachstahl Gmbh | Method for coating steel sheets or steel strips and method for producing press-hardened components therefrom |
DE102017003234A1 (en) | 2017-04-04 | 2018-10-04 | Daimler Ag | Body part for a passenger car, method for coating such a body part and method for producing a coating for such a body part |
US10781962B2 (en) | 2017-08-18 | 2020-09-22 | Baker Hughes, A Ge Company, Llc | Corrosion protection element for downhole connections |
WO2020259842A1 (en) | 2019-06-27 | 2020-12-30 | Thyssenkrupp Steel Europe Ag | Method for producing a coated steel flat product, method for producing a steel component and coated steel flat product |
DE102020002920A1 (en) | 2020-05-15 | 2020-07-02 | Daimler Ag | Procedure for checking a coating |
CA3220573A1 (en) * | 2021-06-04 | 2022-12-08 | Thomas PINGER | Method for producing steel components with resistance to fire |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6511999A (en) * | 1964-09-15 | 1966-03-16 | ||
GB1125965A (en) * | 1964-09-15 | 1968-09-05 | Inland Steel Co | Zinc coating and a method of applying same |
DE2725824A1 (en) * | 1977-06-08 | 1978-12-21 | Fischer Artur Dr H C | COMPONENT FOR THE FORMATION OF AN AXIAL BEARING IN A GAME MODEL |
JPS5891162A (en) * | 1981-11-18 | 1983-05-31 | Nisshin Steel Co Ltd | Manufacture of galvanized steel plate |
JPS58189363A (en) | 1982-04-26 | 1983-11-05 | Nisshin Steel Co Ltd | Manufacture of steel plate coated with alloyed zinc by galvanization |
WO1998026103A1 (en) * | 1996-12-13 | 1998-06-18 | Nisshin Steel Co., Ltd. | HOT-DIP Zn-Al-Mg COATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND SURFACE APPEARANCE AND PROCESS FOR THE PRODUCTION THEREOF |
DE10246614A1 (en) * | 2002-10-07 | 2004-04-15 | Benteler Automobiltechnik Gmbh | Method of making vehicle component with metallic coating from steel sheet or strip, involves coating metal from non-aqueous organic solution before cold forming, hot forming and hardening |
PL2177641T3 (en) | 2003-07-29 | 2013-09-30 | Voestalpine Stahl Gmbh | Steel plate having a galvanized corrosion protection layer |
AT412878B (en) * | 2003-07-29 | 2005-08-25 | Voestalpine Stahl Gmbh | Method for production of a hardened profile part from a hardenable steel alloy having cathodic corrosion protection useful in the production of hardened steel sections, e.g. for automobile construction |
EP1621645A1 (en) * | 2004-07-28 | 2006-02-01 | Corus Staal BV | Steel sheet with hot dip galvanized zinc alloy coating |
CN101027421A (en) * | 2004-06-29 | 2007-08-29 | 克里斯塔尔公司 | Steel sheet with hot dip galvanized zinc alloy coating and process to produce it |
EP1693477A1 (en) * | 2005-02-22 | 2006-08-23 | ThyssenKrupp Steel AG | Coated steel plate |
EP2126144B1 (en) * | 2007-02-23 | 2017-12-27 | Tata Steel IJmuiden BV | Method of thermomechanical shaping a final product with very high strength and a product produced thereby |
-
2007
- 2007-10-10 DE DE102007048504A patent/DE102007048504B4/en not_active Withdrawn - After Issue
-
2008
- 2008-10-10 DE DE202008017609U patent/DE202008017609U1/en not_active Expired - Lifetime
- 2008-10-10 EP EP08802862A patent/EP2195471A1/en not_active Withdrawn
- 2008-10-10 WO PCT/EP2008/008594 patent/WO2009049836A1/en active Search and Examination
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Also Published As
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DE102007048504A1 (en) | 2009-04-16 |
DE202008017609U1 (en) | 2010-01-07 |
DE102007048504B4 (en) | 2013-11-07 |
WO2009049836A1 (en) | 2009-04-23 |
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