EP2888385B1 - Feuille ou bande d'acier revêtue présentant des propriétés avantageuses - Google Patents
Feuille ou bande d'acier revêtue présentant des propriétés avantageuses Download PDFInfo
- Publication number
- EP2888385B1 EP2888385B1 EP13755956.3A EP13755956A EP2888385B1 EP 2888385 B1 EP2888385 B1 EP 2888385B1 EP 13755956 A EP13755956 A EP 13755956A EP 2888385 B1 EP2888385 B1 EP 2888385B1
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- EP
- European Patent Office
- Prior art keywords
- strip
- layer
- steel
- siloxane
- sheet
- 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.)
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- 229910000831 Steel Inorganic materials 0.000 title claims description 71
- 239000010959 steel Substances 0.000 title claims description 71
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 55
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 44
- -1 polysiloxane Polymers 0.000 claims description 35
- 229920001296 polysiloxane Polymers 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 238000003466 welding Methods 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 239000010960 cold rolled steel Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QCYJQMCLPOBYNI-UHFFFAOYSA-N 3,3-bis(trimethoxysilyl)propylurea Chemical compound CO[Si](OC)(OC)C([Si](OC)(OC)OC)CCNC(N)=O QCYJQMCLPOBYNI-UHFFFAOYSA-N 0.000 claims description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000885 Dual-phase steel Inorganic materials 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- FIRQYUPQXNPTKO-UHFFFAOYSA-N ctk0i2755 Chemical compound N[SiH2]N FIRQYUPQXNPTKO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 64
- 238000012360 testing method Methods 0.000 description 19
- 239000011777 magnesium Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 230000032798 delamination Effects 0.000 description 8
- 238000004026 adhesive bonding Methods 0.000 description 6
- 238000005304 joining Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
- 229910000712 Boron steel Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- 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
- C23C2/04—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
-
- 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
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Definitions
- the invention relates to a strip or sheet of cold formable cold rolled steel coated with a zinc alloy layer containing aluminium and magnesium.
- the invention also relates to a method for producing such a steel strip or sheet, to a method for producing a part from the strip or sheet, and to a product comprising a part made from the steel strip or sheet.
- zinc alloy coatings containing aluminium and magnesium are often used in view of their improved corrosion and galling resistance in comparison to galvanized or galvannealed coatings.
- These zinc alloy layers often contain 0.3 - 5 weight% Al and 0.3 - 5 weight% Mg, the remainder being zinc and unavoidable impurities, and optionally at most 0.2 weight % in total of one or more additional elements selected from the group consisting of Pb, Sb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr, Bi, Si and Fe.
- This aluminium and magnesium containing zinc coated steel however has the drawback that the adhesive bonding thereof is less then the adhesive bonding of normal hot dip zinc coated steel. Also the spot weldability of hot dip coatings is often less than that of electrogalvanised steel. Moreover, the aluminium and magnesium containing zinc coatings have a somewhat higher coefficient of friction than normal zinc coatings.
- one or more of these objects is reached with a strip or sheet of cold formable cold rolled steel coated with a zinc alloy layer, wherein the zinc alloy layer contains 0.3 - 5 weight% Al and 0.3 - 5 weight% Mg, the remainder being zinc and unavoidable impurities and optionally at most 0.2 weight % in total of one or more additional elements selected from the group consisting of Pb, Sb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr, Bi, Si and Fe, wherein the zinc alloy layer is coated with a siloxane or polysiloxane layer, the siloxane or polysiloxane layer having a layer thickness corresponding with 1 - 10 mg/m 2 Si.
- the inventors have surprisingly found that with the siloxane or polysiloxane layer as specified above, the joining behaviour of the zinc alloy coated steel is better than the joining behaviour without such a layer, especially the adhesive bonding behaviour, but also the spot weldability.
- the strength and failure mode of adhesive bonded joints of the zinc alloy coated steel provided with a siloxane or polysiloxane layer is better than that of the zinc alloy coated steel without such a siloxane or polysiloxane layer.
- the friction of the zinc alloy coated steel is reduced with at least 10 % with the application of the siloxane or polysiloxane layer, which is advantageous for for instance deep drawing operations.
- the galling behaviour of the zinc alloy coated steel with the siloxane or polysiloxane layer is at least as good as that of the material without such a layer.
- Phosphate coverage of the zinc alloy coated steel that has been coated with a siloxane or polysiloxane layer is as good as phosphate coverage of zinc alloy coated steel without siloxane or polysiloxane layer.
- siloxane or polysiloxane to improve adhesive bonding of aluminium parts is known, but it is not known to use siloxane or polysiloxane for improving the adhesive bonding of zinc or zinc alloy coated steel parts.
- Siloxane or polysiloxane on zinc coated steels is well known to improve corrosion resistance and lacquer adhesion, but for automotive purposes this has not been an option because of spot welding and phosphate forming limitations.
- US 5,433,976 discloses a cold rolled steel strip coated with siloxane.
- WO 2008/102009 A1 discloses a hot dip galvanised cold rolled steel strip coated with a zinc alloy coating layer comprising magnesium and aluminium.
- a siloxane or polysiloxane layer is used on a hot formable zinc or zinc alloy coated steel strip, sheet or blank resulting in a reduction of the oxidation of the zinc layer and a reduction of zinc losses during the hot forming process.
- the siloxane or polysiloxane according to the older patent application is thus used for a different type of steel and for a different process.
- the present invention in contrast relates to cold formable cold rolled steel, not being a steel for hot forming at a temperature of 600° C or above.
- the cold rolled steel has a composition in weight% of:
- the steel strip or sheet has a tensile strength of at most 600 MPa, such as an Interstitial Free steel (IF-steel), a bakehardenable steel or a dual phase steel (DP steel).
- IF-steel Interstitial Free steel
- DP steel dual phase steel
- the zinc alloy layer on the steel has a thickness of 20 - 140 g/m 2 on each side. These zinc alloy thicknesses are generally used in the automotive industry on steel.
- the siloxane or polysiloxane layer has a layer thickness corresponding with 1 - 8 mg/m 2 Si, preferably a thickness of 1 - 5 mg/m 2 Si. It has been found that with these reduced thicknesses the advantages are retained, while it is preferred to use thin layers from an economic perspective.
- the siloxane or polysiloxane layer has been formed from a bis-tri(m)ethoxysilylalkane, preferably a bis-triethoxysilylethane (BTSE), and preferably in combination with another silane such as ⁇ -aminopropyltriethoxysilane ( ⁇ APS), bis-aminosilane (BAS), bis-diaminosilane (BDAS), vinyltriacetoxysilane (VTAS), ⁇ -ureidopropyltrimethoxysilane ( ⁇ UPS) and/or bis-trimethoxysilylpropylurea (BUPS).
- ⁇ APS ⁇ -aminopropyltriethoxysilane
- BAS bis-aminosilane
- BDAS bis-diaminosilane
- VTAS vinyltriacetoxysilane
- ⁇ UPS ⁇ -ureidopropyltrimethoxysilane
- BUPS bis-trimethoxys
- the zinc alloy layer contains 1.0 - 3.5 weight% Al and 1.0 - 3.5 weight% Mg, preferably 1.4 - 2.2 weight% Al and 1.4 - 2.2 weight% Mg.
- These amounts of Al and Mg in the zinc layer usually provide a corrosion protection that is suitable for automotive purposes. Higher amounts make the zinc alloy comparatively expensive and less easy to weld.
- the siloxane or polysiloxane layer is covered by an oil.
- Zinc or zinc alloy coated strip is usually provide with a thin layer of oil before it is supplied to the automotive industry.
- a method for producing a strip or sheet according to the first aspect of the invention is provided in accordance with claim 9. In this way it is relatively easy to apply the siloxane or polysiloxane layer to the zinc alloy coated steel strip or sheet in an environmentally friendly way.
- the silane/silanol containing water based solution contains a fluoride, preferably hydrogen fluoride, fluorosilicic acid, fluorozirconic acid and/or fluorotitanic acid.
- fluorides are added to improve the adhesion of the siloxane or polysiloxane layer to the zinc alloy layer on the steel strip or sheet.
- a method for producing a part from a zinc alloy coated cold rolled steel strip or sheet with a siloxane or polysiloxane layer according to the first aspect of the invention is provided, wherein
- the joining is improved due to the siloxane or polysiloxane layer.
- one or more other parts are made from a strip or sheet according to the first aspect of the invention.
- These parts provide a product that has good joining properties, provided by the siloxane or polysiloxane layer that has been provided on the zinc alloy coated steel strip or sheet.
- An additional advantage is the improved cold forming property of the blanks cut from the steel strip or sheet due to the improved coefficient of friction.
- the product is provided with a phosphate layer, and subsequently with a paint layer.
- the car is usually alkaline cleaned and phosphated to provide a good adhesion for the application of a paint layer.
- a good adhesion will only be obtained when the zinc alloy coating is not hampered by remaining surface contaminants, because the zinc alloy layer must give a good electrochemical reaction with the phosphate solution to result in a fine crystalline, pore-free phosphate layer. It has been found that the applied siloxane or polysiloxane layer does not hinder the forming of a good phosphate layer.
- Steel grade 1 was a cold rolled boron steel having a gauge of 0.7 mm.
- Steel grade 2 was a cold rolled formable steel having a gauge of 0.7 mm.
- the ZnAlMg coating on both steel types was applied on a continuous hot dip galvanising production line where the coating thickness was regulated by nitrogen wiping to about 70 mg/m2 per side (approximately 10 ⁇ m per side).
- the composition of the coating was approximately 1.6 weight% Al and 1.6 weight% Mg, with a small amount of Fe by reaction of the aluminium with the steel strip during hot dip galvanising (about 0.005 - 0.02 weight% Fe), the remainder being zinc with inevitable impurities.
- the coated steel was temper rolled with about 0.8% elongation, with Electro Discharge Texturing (EDT) roughness.
- EDT Electro Discharge Texturing
- a water based solution containing both bis-triethoxysilylethane (BTSE) and aminopropyltriethoxysilane (APS) has been applied on the ZnAlMg coated steel with a chem. coater to provide a (poly)siloxane layer having a thickness of 2 and 12 mg/m 2 Si respectively after drying and/or curing.
- BTSE bis-triethoxysilylethane
- APS aminopropyltriethoxysilane
- the adhesive used was Betamate 1496V of DOW Chemical. Some samples were not re-oiled after cleaning to evaluate the interaction with the oil separately. In general, the oil will be absorbed by the adhesive, making it slightly less strong.
- the strength upon failure of the bond is given in Table 1. This strength depends heavily on the steel grade and its gauge, and can only be compared to a similar reference sample.
- the bond can break in the adhesive (cohesive failure), which is the preferred failure mode. It can also break between the adhesive and the metallic coating (adhesive failure), which is less favourable. Often, the broken bond shows a combination of both failure modes, and the amount of each is estimated visually (in % of the overlap area).
- Table 1 adhesive properties Steel grade Silane (mg/m2) Oil (prelube) Strength bond (kN) of Standard Deviation (kN) % cohesive % adhesive ref1 1 0 no 8,1 0,6 0 100 ref2 1 12 no 7,2 1,1 10 90 #1 2 no 9,7 0,2 30 70 ref3 2 0 no 4,4 0,1 0 100 ref4 2 0 yes 4,2 0,1 0 100 #2 2 2 no 4,8 0,1 60 40 #3 2 2 yes 4,7 0,1 70 30
- the test uses one flat tool and one round tool to develop a high-pressure contact with the sample surfaces.
- the tool material used was DIN 1.3343. 1 g/m2 of Multidraw PL61 of Zeller & Gmelin prelube oil was applied on the samples.
- strips of 50 mm width and 300 mm length were pulled at a speed 20 mm/min between a set of tools pushed together with a normal force of 5 kN.
- the strips were drawn through the tools six times (passes) along a testing distance of 55mm; after each stroke the tools were released and the strips returned to the original starting position in preparation for the next stroke. All tests were conducted at 20°C and performed in triplicate.
- Figure 1 shows the number of passes on the horizontal axis and the friction coefficient on the vertical axis.
- the continuous line shows the results of the tests with a siloxane coating
- the interrupted line shows the results without siloxane coating.
- the results in Figure 1 show that the thin siloxane layer reduces friction, which means a better drawing behaviour.
- Samples having a size of 100x200 mm were phosphated according to automotive standards, with a standard automotive alkaline cleaner, activation and phosphate of Chemetall. The amount of resulting phosphate was determined (by weighing) and the crystal size and homogeneity was checked (by secondary electron microscopy).
- Table 2 Phosphating Steel grade type Silane (mg/m2) Phosphate type (Chemetall) Amount phosphate (g/m2) of Phosphate crystal size and homogeneity ref1 1 0 Spray phosphate GB R2830E3 with 100 - 200 ppm F 3,3 OK ref2 1 12 Spray phosphate GB R2830E3 with 100 - 200 ppm F 2,4 Not OK #1 1 2 Spray phosphate GB R2830E3 with 100 - 200 ppm F 3,5 OK ref3 2 0 Dip phosphated with GB R2600 2,6 OK #2 2 2 2 Dip phosphated with GB R2600 2,3 OK
- the welding range was determined according to StahlEisen SEP 1220 Part 2 for a sample without siloxane and in duplicate for a sample with a thin layer of siloxane (2 mg/m 2 Si) on steel grade 2.
- a standard prelube (1 g/m2 Quaker N6130) was applied on all samples.
- the welding range is the range between the current (Imin) necessary to achieve the minimum welding nugget and the maximum current (Imax) before splashing occurs during welding.
- Imin the current necessary to achieve the minimum welding nugget
- Imax the maximum current
- a larger welding range is a strong indication for a better electrode life, the number of welds before an electrode needs to be replaced to achieve a good weld.
- the minimum and maximum welding currents and the welding range are given in Table 3.
- the welding range of the ZnAlMg coating with the silane (#2 and #3) is larger than the welding range on the same samples without the silane (ref3).
- Table 3 Welding range Steel grade Silane (mg/m2) Imin (kA) Imax (kA) Range (kA) ref3 2 0 8,4 10,1 1,7 #2 2 2 6,8 10,5 3,7 #3 2 2 8,1 10,6 2,5
- the phosphated samples (ref3 and #2 from Table 2) were additionally E-coated with 20-25 ⁇ m Cathoguard 500 from BASF for the following tests:
- the corrosion results can be found in Figure 2 .
- the delamination of the E-coat after the corrosion test is given in millimetres.
- the samples with siloxane layer are denominated A, the samples without siloxane layer are denominated B.
- the visible delamination is indicated in the white stave, the visible plus non-visible delamination is indicated by the dark stave.
- the variance in delamination is indicated in the figure. As can be seen, the difference in corrosion resistance of the ZnAlMg coated steel with and without the siloxane layer is small.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Coating With Molten Metal (AREA)
Claims (14)
- Bande ou feuille d'acier laminé à froid, formable à froid, revêtue d'une couche d'alliage de zinc, la couche d'alliage de zinc contenant 0,3 - 5 % en poids d'Al et 0,3 - 5 % en poids de Mg, le reste étant le zinc et les impuretés inévitables, et optionnellement un maximum de 0,2 % en poids en tout d'un ou plusieurs éléments additionnels sélectionnés dans le groupe constitué de Pb, Sb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr, Bi, Si et Fe, la couche d'alliage de zinc étant revêtue d'une couche de siloxane ou de polysiloxane, la couche de siloxane ou de polysiloxane ayant une épaisseur de couche correspondant à 1-10 mg/m2 Si.
- Bande ou feuille selon la revendication 1, dans laquelle l'acier laminé à froid a une composition en % de poids de :0,001 < C <0,150,01 < Mn < 2,00,001 < Si < 0,5Cr < 1,0Al < 0,5Mo < 0,2Ti < 0,2P < 0,12N < 0,15S < 0,05B < 0,01le reste étant Fe et les impuretés inévitables.
- Bande ou feuille selon la revendication 1 ou 2, dans laquelle l'acier a une résistance maximale à la traction de 600 MPa, tel qu'un acier sans interstitiels (IFS), un acier durcissable à la cuisson ou un acier biphasé (acier DP).
- Bande ou feuille selon la revendication 1, 2 ou 3, dans laquelle la couche d'alliage de zinc sur l'acier a une épaisseur de 20 - 140 g/m2 de chaque côté.
- Bande ou feuille selon l'une quelconque des revendications précédentes, dans laquelle la couche de siloxane ou de polysiloxane a une épaisseur de couche correspondant à 1 - 8 mg/m2 Si, de préférence une épaisseur de 1 - 5 mg/m2 Si.
- Bande ou feuille selon l'une quelconque des revendications précédentes, où la couche de siloxane ou de polysiloxane a été formée à partir d'un bis-tri(m)éthoxysilylalkane, de préférence un bis-triéthoxysilyléthane (BTSE), et de préférence en combinaison avec un autre silane tel que : γ-aminopropyltriéthoxysilane (γAPS), bis-aminosilane (BAS), bis-diaminosilane (BDAS), vinyltriacétoxysilane (VTAS), γ-ureidopropyl-triméthoxysilane (γUPS) et/ou bis-triméthoxysilylpropylurée (BUPS).
- Bande ou feuille selon l'une quelconque des revendications précédentes, dans laquelle la couche d'alliage de zinc contient 1,0 - 3,5 % en poids d'Al et 1,0 - 3,5 % en poids de Mg, de préférence 1,4 - 2,2 % en poids d'Al et 1,4 - 2,2 % en poids de Mg.
- Bande ou feuille selon l'une quelconque des revendications précédentes, dans laquelle la couche de siloxane ou de polysiloxane est couverte d'une huile.
- Procédé de production d'une bande ou feuille selon l'une quelconque des revendications précédentes, dans lequel la couche de siloxane ou de polysiloxane est formée en fournissant à la couche d'alliage de zinc une solution à base d'eau contenant du silane/silanol appliquée par immersion et/ou pulvérisation avec compression additionnelle, ou par laminage suivi de séchage et/ou durcissement.
- Procédé selon la revendication 9, dans lequel la solution à base d'eau contenant du silane/silanol contient un fluorure, de préférence : fluorure d'hydrogène, acide fluorosilicique, acide fluorozirconique et/ou acide fluorotitanique.
- Procédé pour produire une pièce à partir d'une bande ou feuille selon l'une quelconque des revendications 1-8, dans lequel- un flan est découpé dans la bande ou la feuille- le flan est placé dans un outil de formage, tel qu'une presse- le flan est formé à froid pour devenir une pièce.
- Produit réalisé à partir d'une pièce fabriquée à partir de la bande ou feuille selon l'une quelconque des revendications 1-8 et d'une ou plusieurs autres pièces, dans lequel la pièce réalisée à partir de la bande ou de la feuille est jointe à au moins une des autres pièces au moyen d'un soudage par points et/ou d'un mastic ou d'un adhésif.
- Produit selon la revendication 12, dans lequel une ou plusieurs autres pièces sont fabriquées à partir d'une bande ou feuille selon l'une quelconque des revendications 1-8.
- Produit selon la revendication 12 ou 13, le produit recevant une couche de phosphate, puis une couche de peinture.
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EP13755956.3A EP2888385B1 (fr) | 2012-08-27 | 2013-08-19 | Feuille ou bande d'acier revêtue présentant des propriétés avantageuses |
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EP12006485 | 2012-09-14 | ||
PCT/EP2013/002498 WO2014032779A1 (fr) | 2012-08-27 | 2013-08-19 | Bande ou tôle d'acier revêtu ayant des propriétés avantageuses |
EP13755956.3A EP2888385B1 (fr) | 2012-08-27 | 2013-08-19 | Feuille ou bande d'acier revêtue présentant des propriétés avantageuses |
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EP2888385B1 true EP2888385B1 (fr) | 2018-04-11 |
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EP (1) | EP2888385B1 (fr) |
ES (1) | ES2672698T3 (fr) |
TR (1) | TR201807970T4 (fr) |
WO (1) | WO2014032779A1 (fr) |
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TR201807970T4 (tr) | 2012-08-27 | 2018-06-21 | Tata Steel Ijmuiden Bv | Avantajlı özelliklere sahip kaplanan çelik şerit veya levha. |
US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
KR101819393B1 (ko) * | 2016-12-22 | 2018-01-16 | 주식회사 포스코 | 용접성 및 프레스 가공성이 우수한 용융 아연계 도금강재 및 그 제조방법 |
US11905579B1 (en) | 2019-09-30 | 2024-02-20 | Thyssenkrupp Steel Europe Ag | Sheet steel having a deterministic surface structure |
DE102019215051A1 (de) * | 2019-09-30 | 2021-04-01 | Thyssenkrupp Steel Europe Ag | Stahlblech mit einer deterministischen Oberflächenstruktur |
CN113234996A (zh) * | 2021-04-15 | 2021-08-10 | 首钢集团有限公司 | 一种高强if的冶炼方法 |
CN114226147B (zh) * | 2021-12-18 | 2023-07-11 | 新万鑫(福建)精密薄板有限公司 | 一种取向硅钢极薄带绝缘层涂覆方法 |
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- 2013-08-19 TR TR2018/07970T patent/TR201807970T4/tr unknown
- 2013-08-19 ES ES13755956.3T patent/ES2672698T3/es active Active
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Publication number | Publication date |
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TR201807970T4 (tr) | 2018-06-21 |
EP2888385A1 (fr) | 2015-07-01 |
WO2014032779A8 (fr) | 2015-05-21 |
ES2672698T3 (es) | 2018-06-15 |
WO2014032779A1 (fr) | 2014-03-06 |
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