EP2851452A1 - Anorganische Karbonat- basierende Konversionssschicht auf verzinktem Stahl - Google Patents
Anorganische Karbonat- basierende Konversionssschicht auf verzinktem Stahl Download PDFInfo
- Publication number
- EP2851452A1 EP2851452A1 EP13004572.7A EP13004572A EP2851452A1 EP 2851452 A1 EP2851452 A1 EP 2851452A1 EP 13004572 A EP13004572 A EP 13004572A EP 2851452 A1 EP2851452 A1 EP 2851452A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- carbonate
- suspension
- steel sheet
- supplier
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims description 36
- 239000010959 steel Substances 0.000 title claims description 36
- 238000007739 conversion coating Methods 0.000 title description 2
- 229910052806 inorganic carbonate Inorganic materials 0.000 title 1
- 239000010410 layer Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 54
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 44
- 239000008397 galvanized steel Substances 0.000 claims abstract description 44
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002346 layers by function Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- -1 alkali metal bicarbonates Chemical class 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 8
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000012254 magnesium hydroxide Nutrition 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims abstract description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 239000011734 sodium Substances 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 21
- 230000007797 corrosion Effects 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000000314 lubricant Substances 0.000 claims description 15
- 239000000700 radioactive tracer Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000007900 aqueous suspension Substances 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000010687 lubricating oil Substances 0.000 claims description 7
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000001226 triphosphate Substances 0.000 claims description 6
- 235000011178 triphosphate Nutrition 0.000 claims description 6
- 238000004876 x-ray fluorescence Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000002264 triphosphate group Chemical group [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 235000014692 zinc oxide Nutrition 0.000 claims description 4
- 238000010073 coating (rubber) Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000019351 sodium silicates Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009189 diving Effects 0.000 claims 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims 1
- 239000001120 potassium sulphate Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 238000011282 treatment Methods 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 238000005461 lubrication Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005246 galvanizing Methods 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052599 brucite Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 208000009043 Chemical Burns Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000282485 Vulpes vulpes Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- ZPUBJHQABOZYOK-UHFFFAOYSA-L aluminum zinc carbonate Chemical compound C([O-])([O-])=O.[Zn+2].[Al+3] ZPUBJHQABOZYOK-UHFFFAOYSA-L 0.000 description 1
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical class [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- RYSQYJQRXZRRPH-UHFFFAOYSA-J tin(4+);dicarbonate Chemical compound [Sn+4].[O-]C([O-])=O.[O-]C([O-])=O RYSQYJQRXZRRPH-UHFFFAOYSA-J 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the present invention relates to a galvanized steel sheet having an inorganic functional layer and a method for producing the coated galvanized steel sheet. Furthermore, the invention relates to the use of a treatment solution for producing the functional layer and the use of the steel sheet for the production of motor vehicle components.
- Electrolytically galvanized and hot-dip galvanized sheet steel has been established from the mid-1980s until today as an essential pillar of corrosion protection for high-quality car bodies.
- Zinc-protected surfaces today ensure such high corrosion resistance that the useful life of the entire vehicle is no longer decisively limited by corrosion.
- Electrolytically galvanized steel has been used for years in the automotive body shop.
- the surface finish is applied before galvanizing ("temper rolling").
- the softer zinc layer is subsequently uniformly deposited by electrolysis on the hard base metal.
- the elo-galvanized strip can be phosphated.
- Vorphosphatierung acts as a solid lubricant, reduces friction and prevents welding of the zinc on the tool.
- Prelube oils are used for pre-phosphated sheet metal. Ribbons and sinkers are often washed with low viscosity Prelube oils. A relubrication with drawing oils is only exceptionally necessary.
- Another possibility for improving the formability is the coating with dry lubricant (Drylube, Hotmelt) instead of the Prelubeöle.
- Release layers or tribo layers applied to the surface of galvanized steel must be compatible with the raw building adhesives used for automotive use.
- WO 2005/071140 A1 the use of an aqueous treating solution containing sulfate ions in a concentration of at least 0.01 mol / l is known to treat the surface of a galvanized steel sheet to reduce damage to the coating during forming and for temporarily improved corrosion protection.
- ArcelorMittal has developed such a tribo coating for fire zinc plates and launched it under the name "NIT". This layer is characterized by a very good friction reduction with good adhesive adhesion.
- electrolytically galvanized sheet has been proven in addition to oiling a tri-cation tape phosphating. This is similar to the later applied in the Lackierline tri-cation phosphating.
- DE 102008016050 A1 describes a primer for forming a forming layer, metal substrates coated with this primer and the use of the primer and the coated substrates.
- the primers contain binders, additives, anticorrosive pigments, crosslinking agents and solvents. Branched polyester resins or other resins may be used as the binder, and anticorrosive pigments may be calcium modified silica, zinc phosphates, aluminum phosphates, aluminum triphosphates, silica-magnesium pigments and mixtures.
- WO 2004/050808 A1 discloses a lubricant coated sheet metal having improved forming properties.
- the coating lubricant is a corrosion protection oil, a so-called Prelube oil and / or a dry lubricant (Drylube, Dry Film Lubricant), wherein the metal sheet is a layer which is formed by applying a solution containing an organic phosphoric acid ester on the surface of the sheet.
- a solution containing the organic phosphoric acid ester is applied to the top and / or bottom of the sheet and then the lubricant is applied to the sheet thus coated.
- the solution can be applied by dipping, spraying, brushing or knife coating.
- insufficient process compatibility in automotive engineering still limits the use.
- the present invention Based on this prior art, the present invention, the object of the time-economic and in existing manufacturing processes, especially in automotive integrable production of a galvanized steel sheet with a functional layer to allow in terms of formability in comparison to only oiled surfaces, especially at high Contact pressures and high temperatures, is significantly improved, and can be economically applied on a large scale and is safe in terms of environment, health and safety.
- Another object is to provide the galvanized steel sheet with functional layer, which is significantly improved in terms of formability compared to only oiled surfaces, especially at high contact pressures and high temperatures.
- the functional layer should be insoluble or compatible with subsequently sprayed on lubricating oil.
- the functional layer should also show a good adhesion of structural adhesive and suitable for body pretreatment (phosphating and phosphate-free process) and KTL-compatible.
- Claim 12 discloses the use of the coated galvanized steel sheet in automobile construction.
- claim 13 discloses the use of a solution or suspension to produce the inorganic functional layer on galvanized steel.
- a method according to the invention for the time-economic production of a galvanized steel sheet having an inorganic functional layer on the surface forming a Umformanges slaughter or part of a Umformologis slaughter begins with the preparation of an aqueous, silane-free (silane-free) solution or suspension containing at least one carbonate Supplier or at least one carbonate supplier and at least one hydroxide supplier.
- carbonate or “hydroxide supplier” refers to salts which are at least partially soluble in aqueous medium and dissociate, so that the desired zinc salts are formed on the galvanized surface by chemical reaction in the aqueous treatment solution or suspension become.
- the carbonate supplier (s) are selected from ammonium bicarbonate, ammonium carbonate, alkali metal bicarbonates, alkali metal carbonates, and alkali metal carboxylates
- the hydroxide source (s) are selected from alkali metal hydroxides, alkali metal oxides, alkali metal alkoxides, and magnesium hydroxide or magnesium oxide.
- an additional hydroxide supplier can advantageously be dispensed with if the carbonate supplier goes into solution with the formation of hydroxide ions in an aqueous medium, as described, for example, in US Pat. B. with alkali metal bicarbonates and alkali metal carbonates is the case.
- a concentration of the carbonate supplier (s) required in the solution or suspension to form the conversion layer is in a range from 1 to 5% by weight, preferably from 3 to 5% by weight.
- the pH of the aqueous solution or suspension is in the range from 7 to 13, preferably from 8 to 12. It has been found that a pH of (9 ⁇ 0.5) leads to particularly suitable conversion layers. Depending on the type of carbonate or hydroxide suppliers selected, the pH of the treatment solution or suspension may already be within the stated range; however, if desired or required, addition of sodium hydroxide and / or potassium hydroxide may be made to adjust the pH.
- the aqueous solution or suspension is applied to at least one side of the galvanized steel sheet and thus a wet film is produced with a thickness of 1 to 20 microns, so that at the surface a chemical reaction of the metallic coating with the at least partially dissolved in the aqueous medium and Dissociated carbonate suppliers or hydroxide suppliers to form zinc salts takes place.
- a conversion layer of zinc salts which are at least partially carbonates, is then obtained as the inorganic functional layer.
- the layer weight of the dry substance after drying of the wet film is advantageously in a range from 25 to 200 mg / m 2 surface, preferably from 40 to 90 mg / m 2 and is thus suitable for the desired further processing.
- a deposited dry matter of 40 to 90 mg / m 2 surface is obtained, which converts to hydrozincite.
- the coating weight of the conversion layer is in a range of 190 to 340 mg / m 2 and thus has a favorable and suitable strength for the intended purpose.
- the hot-dip galvanized or elo-galvanized steel sheets with the functional layer can be economically produced with a small amount of time and equipment.
- This treatment solution or suspension advantageously contains neither heavy metals nor organic compounds or solvents.
- alkaline Solutions related risks are known and can be managed well; necessary protective measures against chemical burns are limited.
- this conversion layer is oil resistant and soluble only in acids. The conversion layer shows good adhesion of raw building adhesives and is suitable for car body pretreatment and KTL-compatible.
- any alkali element can generally be used as a cation of the carbonate and hydroxide suppliers, but mainly for cost and availability reasons, sodium and / or potassium will preferably be used.
- Particularly preferred as carbonate suppliers are sodium and / or potassium bicarbonate and / or carbonate and used as hydroxide suppliers sodium or potassium hydroxide.
- a treatment solution or suspension with these components achieves conversion layers with an optimum combination of friction behavior and bondability.
- the application of the aqueous solution or suspension to the galvanized steel sheet can generally be done by spraying without squeezing or jetting and stripping with non-driven squeeze rolls.
- the aqueous solution or suspension by rolling continuously applied to a strip of galvanized sheet steel.
- a roller coater which usually works per coating side with two or three rollers (scoop roller, application roller and possibly regulating roller), wherein the tape is deflected at the counter-pressure roller.
- the aqueous solution or suspension can be rolled up in a time-economical manner by means of two squeeze rolls, between which the hot-dip galvanized steel sheet or steel strip is guided, in a simple and thus preferred manner.
- the aqueous solution or suspension is sprayed in excess onto the squeezing rollers arranged on both sides of the galvanized steel sheet and excess solution or suspension, which drips off the sheet or the rollers, is collected and guided into a feed tank.
- the squeeze rolls are pressurized against the surfaces of the galvanized steel sheet, thereby stripping the aqueous solution or suspension onto the surfaces of the galvanized steel sheet.
- the thickness of the wet film is set in a range of 1 to 20 ⁇ m by selecting the setting pressure, a hardness of rubberizing the squeezing rollers, a speed of the squeezing rollers and a speed of the steel sheet and thus a relative speed of the squeezing rollers to the steel sheet.
- a corrosion protection oil and / or a Prelubeöls or a dry lubricant carried on the conversion layer, so that a lubricating oil layer having a basis weight of 0.2 to 3.0 g / m 2 is obtained.
- An inventive hot-dip galvanized steel sheet has on the surface an inorganic functional layer which forms a forming auxiliary layer or is part of a forming auxiliary layer.
- the inorganic functional layer according to the invention is based on an alternative chemical basis. It is a conversion layer formed from zinc and zinc salts, of which at least a part of the Carbonates heard.
- the conversion layer is obtained by applying a treatment medium to the galvanized sheet steel surface, which is an aqueous solution or suspension free of hydrogen sulphide, which contains at least one carbonate supplier, but preferably at least one carbonate supplier and additionally at least one hydroxide supplier.
- the zinc salts of the conversion layer may further include zinc hydroxides and zinc oxides; the conversion layer can therefore preferably have a hydrozincite-like mineral structure.
- the conversion layer with a method according to the invention can be displayed time-economically.
- the layer weight of the dry substance which leads to the formation of the conversion layer is from 25 to 200 mg / m 2 surface, preferably from 40 to 90 mg / m 2 , a sufficiently good formability is ensured.
- a tracer system can be provided in the conversion layer, which can be detected by X-ray fluorescence analysis and is selected from potassium, phosphorus, silicon or even tin or titanium compounds.
- the Umformins slaughter the hot-dip galvanized steel sheet also has a lubricating oil layer, which is applied to the conversion layer, which in itself shows only limited anti-corrosion and lubricating effect.
- This lubricating oil layer has a basis weight of 0.2 to 3.0 g / m 2 , typically 1.0 -1.5 g / m 2 , and thus meets the current delivery instructions for oiled steel strip.
- the conversion layer is compatible with subsequently sprayed on corrosion protection oil or Prelube oil or dry lubricants and their suitability for subsequent process steps such as adhesive bonding or removability in automotive shell construction does not affect.
- the application of corrosion protection or prelube oil or dry lubricant is for corrosion protection and lubrication necessary during forming.
- the terms "conversion layer” and "functional layer” are used synonymously. While the term “conversion layer” is used more in the context of chemical composition and formation process, the term “functional layer” is more likely to be associated with the effect of this layer (in subsequent process steps).
- a coated galvanized steel sheet according to the invention can be used in particular for producing a motor vehicle component, wherein the steel sheet is subjected to one or more forming steps.
- the conversion layer applied to the galvanized sheet steel as a tribo layer is suitable for use in the automotive industry; and also the application of the treatment solution can be industrially implemented in mass production.
- an aqueous solution or suspension of at least one carbonate supplier or an aqueous solution or suspension of at least one carbonate supplier and at least one hydroxide supplier allows the formation of a conversion layer as an inorganic functional layer or tribo layer on the surface of a galvanized steel sheet.
- the carbonate supplier (s) are selected from ammonium bicarbonate, ammonium carbonate, alkali metal hydrogencarbonates, alkali metal carbonates, and alkali metal carboxylates
- the hydroxide source (s) are selected from alkali metal hydroxides, alkali metal oxides, alkali metal alcoholates, and magnesium hydroxides or magnesium oxide.
- solids with a lattice structure should be particularly suitable for reducing the solid-state friction, in which the combination of the structure-forming layers with one another is significantly weaker in one spatial direction than in the layer plane. This property is found z.
- MoS 2 molybdenum disulfide
- h-BN hexagonal boron nitride
- such solids are generally not suitable for use on sheet metal surfaces for automobile bodies, since they exert a separating effect on the adhesives used in the shell.
- the above-mentioned substances have low surface energies and are insoluble in the treatment baths used for cleaning and pretreating the body panels, which would lead to poor results in the structure of the paint job.
- a suitable mineral is brucite, which consists of magnesium hydroxide, Mg (OH) 2 . It forms a layer grid of the Cdl 2 type (where the iodide ions form a hexagonal close-packed spherical packing, the octahedral gaps of every second interlayer space are completely filled with cadmium ions) with pronounced cleavage in one spatial direction, but in contrast to graphite, molybdenum disulfide or hexagonal boron nitride has no markedly low surface energies and is soluble in processing baths because of its predominantly ionic bonding character.
- the functional or conversion layer to be produced on the galvanized steel surface ensures the reduction of the friction during forming of the steel sheet.
- the conversion layer is formed by the reaction of the surface-dried solution described above with the metal surface.
- the thickness of the conversion layer thus results from the concentration of the treatment solution and the thickness of the applied wet film.
- the basis weight of the dry substance is 25 to 200 mg / m 2 , preferably 40 to 90 mg / m 2 .
- the pH of the treatment solution or suspension should be 7 to 13, in particular 8 to 12.
- the solutions or suspensions of the carbonate or hydroxide suppliers may contain cations of the elements lithium, sodium, potassium, rubidium, cesium, but preferably sodium and potassium, and magnesium hydroxide or oxide.
- the treatment solution may contain as an additive a tracer system which, although not required to obtain the tribological effect, serves as an indicator for the quantitative detection of the applied amount and does not hinder the formation of the conversion layer.
- a tracer system which, although not required to obtain the tribological effect, serves as an indicator for the quantitative detection of the applied amount and does not hinder the formation of the conversion layer.
- substances of the following elements can be used: potassium, phosphorus, silicon, tin or titanium. These elements can be detected more easily than the element sodium by X-ray fluorescence analysis (RFA).
- the compounds potassium carbonate / bicarbonate, Na / K phosphate or Na / K di- (tri-phosphates, alkali silicate (especially sodium silicate, potassium silicate) tin carbonate / bicarbonate may preferably be used for this purpose to 1.5 wt .-% of the respective tracer system, preferably 0.05 to 1 wt .-%.
- the application of the solution or suspension can generally be done by dipping, spraying, spraying / squeezing, roller coater or combinations of these methods with subsequent drying - of course, or thermally assisted.
- the galvanized sheet steel coated according to the invention has a reduced coefficient of friction, wherein in addition the stick-slip behavior is avoided or at least reduced. Furthermore, the transfer of material from the workpiece to the tool and the formation of metal abrasion is reduced. On the other hand, the paintability and adhesiveness of the surface is retained.
- the galvanized sheet steel coated according to the invention is wash-resistant to wash oils, while the conversion layer is very readily wettable with water.
- the Fig. 1 shows a preferred simple method for producing a friction-reducing coated steel sheet according to the invention.
- the sketched for carrying out the process plant can be roughly divided into three steps, jetting, squeezing and drying.
- the galvanized steel strip 1 is moved in accordance with the feed direction a and guided between the rubberized squeegee rollers 10, which are located above and below the Steel strip 1 are located.
- the treatment solution L (or suspension) is sprayed in excess onto the rubber coating 11 of the squeeze rollers 10.
- the excess of the processing solution L at the squeegee 10 above the steel strip 1 flows first onto the steel strip 1, then over the strip edge in the receiver 13, while the excess of the treatment solution L at the squeegee 10 below the steel strip 1 directly from the roller 10 back into the storage container 13 passes. From the reservoir 13, the treatment solution L is supplied to the appropriate application lines 14 the application devices 12.
- the self-propelled squeeze rolls 10 are placed on the surfaces of the steel strip 1 with pneumatic or hydraulic pressure and strip the excess processing solution L thereon.
- the upper roller serves as an abutment for the lower roller and vice versa.
- the Anstelldrucks the hardness of the rubber coating 11, the relative speed of the squeeze rollers 10, which rotate at speed b, the steel strip 1 and the speed a of the steel strip 1 wet films 2 'of 1 to 20 microns, but preferably 2 to 3 microns produced become. Thinner wet films may be preferred as they allow shorter dryer runs, lower belt temperatures, or faster belt speeds.
- the wet film 2 ' is dried in a circulating air dryer 15, so that the functional layer 2 is obtained on the hot-dip galvanized steel strip surface. Between outlet squeeze rollers 10 and outlet circulating air dryer 15, the steel strip 1 is tensioned without support.
- the wet film can also be air-dried.
- Construction and arrangement of the application device may well differ from the example shown.
- roller coater As an alternative to the example shown, the application by a equipped with two or three rollers Rollcoater conceivable that greater freedom in the Allow design of the wet film regardless of the belt speed. Rollcoaters are also part of the standard equipment for many systems, especially for the inline coating of antifinger printing. However, since roller coater cause significantly higher investment, maintenance and operating costs, they are used for simple post-treatments, as it represents the application of the treatment solution according to the invention, less frequently.
- sodium and potassium carbonate and bicarbonate or sodium and potassium bicarbonate and hydroxide are selected with a total concentration in the treatment solution of 3 to 5 wt .-% and the pH in a range of 7 to 13, preferably 8 to 12, more preferably set to 9.
- the pH of the treatment solution should be in a range from 7 to 13, preferably 8 to 12, more preferably about 9, and is optionally adjusted, preferably with NaOH or KOH.
- the exemplary process described here of forming conversion layers by the action of basic alkali metal carbonates on galvanized steel surfaces provides for the formation of structures which resemble the hydrozincite Zn 5 [(OH) 6
- the wet film applied to the metal surface according to the invention is dried and subsequently not rinsed with water. Therefore, all non-volatile components remain on the surface.
- the layer weight of the dry substance is in a range of 25 to 200 mg / m 2, preferably 40 to 90 mg / m 2 .
- the layer weight of the forming conversion layer is correspondingly larger due to corrosion and incorporation of the zinc, aluminum or magnesium from the sheet surface.
- the coating weight of the dry substance can be determined by the thickness of the wet film as a function of the concentration of the treatment solution. For example, a wet film of a 3% solution is to be applied 1.3 to 3.0 ⁇ m thick in order to achieve the preferred basis weight of the dry matter of 40 to 90 mg / m 2 .
- the layer thickness can be checked by X-ray fluorescence analysis of the added to the solution and present in the dry substance tracer elements potassium, phosphorus, sulfur or silicon, tin, titanium.
- the friction-reducing effect of the conversion layer can be detected, for example, by strip drawing experiments based on VDA 230-213 and by cup draw tests, as described below with reference to FIGS FIGS. 2 to 4 will be shown.
- treatment solutions used to treat the sheets for strip pulling tests and cupping tests are listed in the table below.
- Table 1 Examples of treatment solutions: description
- Treatment or aqueous treatment solution FG TS [mg / m 2 ] EMERGENCY untreated - NC 5% by weight NaHCO 3 / NaOH, pH 9 70 KC 5% by weight KHCO 3 / KOH, pH 9 70 NC + KC 4.25% NaHCO 3 + 0.75% KHCO 3 / NaOH, pH 9 70 NC + PH 4.25% NaHCO 3 + 0.75% Na tripolyphosphate / NaOH, pH 9 70 NC + S 4.25% NaHCO 3 + 0.75% Na 2 SO 4 / NaOH, pH 9 70 NC + Si 4.25% NaHCO 3 + 0.75% Na metasilicate / NaOH, pH 9 70 NC + SiO 2 4.25% NaHCO 3 + 0.75% SiO 2 dispersion Aerodisp W 7520 N (Evonik, Hanau) / NaOH, pH 9 70 H 2
- the 5% strength by weight treatment solution having a pH of 9 is obtained by dissolving 50 g of NaHCO 3 in 950 g of demineralized water and then the solution with sodium hydroxide solution (eg with 50% by weight of NaOH) pH 9 is adjusted.
- Fig. 2 shows in a graph in which the friction coefficient is plotted against the contact pressure, results for flat-strip stripping experiments, on a treated with 5 wt .-% NaHCO 3 / NaOH aqueous solution (pH 9) NC sheet and a 5 wt. % KHCO 3 / KOH aqueous solution (pH 9) treated sheet KC (see Table 1) and for comparison on an untreated sheet NOT according to VDA 230-213 were performed.
- the maximum punch force on the untreated sheet NOT is plotted against the differently pretreated sheet according to Table 1.
- Both treated sheets NC pH 11.5 and NC pH 8.6 surprisingly require a significantly reduced maximum punch force in the cup drawing test in comparison to that Untreated sheet NOT, wherein the treated at pH 8.6 sheet NC pH 8.6 performs even better than the treated at pH 11.5 sheet NC pH 11.5, resulting from the fact that at pH 8.6 the formation of the tribological particularly effective hydrozincite Zn 5 [(OH) 6 (CO 3 ) 2 ] thermodynamically preferred, while at pH 11.5, the formation of the less effective zinc oxide and hydroxide takes place.
- the conversion layer is compatible with a subsequent manufacturing process of a car body shell:
- the temporary corrosion protection of the steel sheet is indispensable for the storage and transport of steel coils and still unpainted pressed parts. This is usually achieved by applying anti-corrosive or Prelube oils or waxy hotmelt dry lubricants in the rolling mill.
- the proof of the corrosion protection properties can be carried out by way of example by means of a condensed water climate test, as described in the test specification VDA 230-213.
- the Prelube Anticorit PL 3802-39 S used for lubrication has been used for years for coil lubrication in the German steel and automotive industry. It can therefore be assumed that the conversion coatings are suitable for the temporary corrosion protection of coils and pressed parts.
- a good adhesion of the adhesives used is essential for the carcass shell.
- the compatibility of the conversion layer with such structural adhesives can be investigated by way of example with an adhesive bead test.
- the adhesive bead is mechanically peeled off and the surfaces of the sheet and the removed bead are examined.
- a retention of adhesive residues on the metal surface indicates good adhesion of adhesive metal.
- Such good adhesion is accompanied by a rough, and thus whitish surface of the adhesive bead.
- the adhesives used were, for example, the products Betamate TM 1496 F and Betamate TM 1040 from Dow Automotive.
- the adhesion properties of the test sheets with conversion layer advantageously correspond to those without such pretreatment (NOT).
- a cohesive (CF) or near-surface cohesive (SCF) fracture pattern was achieved in all cases.
- the adhesive beads cured on the sheets were subjected to corrosion before peeling.
- moisture loads were carried out over a period of 504 h at 50 ° C and 95% relative humidity. It was found that the fracture pattern after the corrosion load is also cohesive (CF) or near-surface cohesive (SCF).
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ES13004572T ES2734456T3 (es) | 2013-09-19 | 2013-09-19 | Capa funcional inorgánica sobre acero galvanizado por inmersión en caliente como ayuda para la conformación |
PL13004572T PL2851452T3 (pl) | 2013-09-19 | 2013-09-19 | Nieorganiczna powłoka funkcyjna na stali ocynkowanej ogniowo jako pomocna przy formowaniu |
EP13004572.7A EP2851452B1 (de) | 2013-09-19 | 2013-09-19 | Anorganische Funktionsschicht auf feuerverzinktem Stahl als Umformhilfe |
PCT/EP2014/002550 WO2015039762A1 (de) | 2013-09-19 | 2014-09-19 | Anorganische karbonat- basierende konversionssschicht auf verzinktem stahl |
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WO2015197430A1 (en) * | 2014-06-27 | 2015-12-30 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
WO2017125131A1 (de) | 2016-01-19 | 2017-07-27 | Thyssenkrupp Steel Europe Ag | Verfahren zum herstellen eines stahlprodukts mit einer zn-beschichtung und einer darauf aufgetragenen tribologisch aktiven schicht sowie entsprechend beschaffenes stahlprodukt |
WO2020064548A1 (de) | 2018-09-24 | 2020-04-02 | Thyssenkrupp Steel Europe Ag | Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden |
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CN110546303A (zh) | 2017-03-30 | 2019-12-06 | 塔塔钢铁艾默伊登有限责任公司 | 用于处理金属表面的含水酸性组合物、使用这种组合物的处理方法和经处理的金属表面的用途 |
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WO2015197430A1 (en) * | 2014-06-27 | 2015-12-30 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
EP3161176B1 (en) | 2014-06-27 | 2018-12-19 | Henkel AG & Co. KGaA | Dry lubricant for zinc coated steel |
US10287665B2 (en) | 2014-06-27 | 2019-05-14 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
WO2017125131A1 (de) | 2016-01-19 | 2017-07-27 | Thyssenkrupp Steel Europe Ag | Verfahren zum herstellen eines stahlprodukts mit einer zn-beschichtung und einer darauf aufgetragenen tribologisch aktiven schicht sowie entsprechend beschaffenes stahlprodukt |
US11078573B2 (en) | 2016-01-19 | 2021-08-03 | Thyssenkrupp Ag | Method for producing a steel product with a Zn coating and a tribologically active layer deposited on the coating, and a steel product produced according to said method |
WO2020064548A1 (de) | 2018-09-24 | 2020-04-02 | Thyssenkrupp Steel Europe Ag | Verfahren zur verbesserung der phosphatierbarkeit von metallischen oberflächen, welche mit einer temporären vor- bzw. nachbehandlung versehen werden |
Also Published As
Publication number | Publication date |
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EP2851452B1 (de) | 2019-04-17 |
WO2015039762A1 (de) | 2015-03-26 |
ES2734456T3 (es) | 2019-12-10 |
PL2851452T3 (pl) | 2019-10-31 |
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