EP3097221A1 - Method for coating metal surfaces, substrates coated in this way, and use thereof - Google Patents
Method for coating metal surfaces, substrates coated in this way, and use thereofInfo
- Publication number
- EP3097221A1 EP3097221A1 EP15703001.6A EP15703001A EP3097221A1 EP 3097221 A1 EP3097221 A1 EP 3097221A1 EP 15703001 A EP15703001 A EP 15703001A EP 3097221 A1 EP3097221 A1 EP 3097221A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- ions
- content
- calculated
- aqueous
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000758 substrate Substances 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title abstract description 7
- 239000002184 metal Substances 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 75
- 150000002500 ions Chemical class 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 230000002378 acidificating effect Effects 0.000 claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- -1 sulphonate anions Chemical class 0.000 claims abstract description 25
- 229920000620 organic polymer Polymers 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 18
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000007739 conversion coating Methods 0.000 claims description 25
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- 150000001768 cations Chemical class 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000003973 paint Substances 0.000 claims description 13
- 239000012487 rinsing solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000010276 construction Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000004922 lacquer Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 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 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000013615 primer Substances 0.000 claims description 4
- 239000002987 primer (paints) Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000004876 x-ray fluorescence Methods 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000011089 mechanical engineering Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 46
- 239000011701 zinc Substances 0.000 description 34
- 239000010410 layer Substances 0.000 description 31
- 239000011572 manganese Substances 0.000 description 24
- 238000007792 addition Methods 0.000 description 23
- 230000007797 corrosion Effects 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 21
- 235000021317 phosphate Nutrition 0.000 description 21
- 229910052725 zinc Inorganic materials 0.000 description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000010960 cold rolled steel Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical class [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002888 zwitterionic surfactant 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
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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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the invention relates to a process for the coating of metallic surfaces with an optionally colored conversion layer, in particular for the replacement of an alkali phosphating such as e.g. an iron phosphating, correspondingly coated substrates with metallic surfaces and the use of these coated substrates.
- an alkali phosphating such as e.g. an iron phosphating
- the fresh, not yet used alkali metal phosphate solutions usually have virtually no or only a very low content of aluminum, iron and zinc.
- the aqueous acidic alkali metal phosphate solutions contain, in addition to ions of at least one alkali metal or / and ammonium, also phosphate ions and, due to the staining effect of these solutions on the metallic surfaces, ion contents of the metals dissolved out of the metallic surfaces, e.g. Aluminum, iron or / and zinc as well as traces of alloy components of the recommended metallic materials.
- the phases mainly formed in the alkali phosphate layer in alkali phosphating are the corresponding phosphates, oxides or / and hydroxides of the metals from the surfaces of the base substrates to be treated.
- Alkaline phosphate solutions or coatings are also referred to as iron phosphate solutions or coatings when used on iron and steel materials.
- alkali phosphate coatings are generally also referred to as layers of the so-called “non-layer-forming phosphating". This designation is misleading since layers are also formed here, but they are significantly thinner than other phosphate layers such as the different types of zinc phosphating.
- the alkali phosphate solution always contains an increased content of at least one alkali metal such as sodium or / and ammonium.
- Alkaline phosphations can usually be carried out in a simple and inexpensive manner.
- high quality alkali phosphate coatings show only limited corrosion protection, usually a) not better than, i.e., better than, corrosion protection.
- the object was to find aqueous compositions which can be applied in a simple manner, which are composed as environmentally friendly as possible and which give a higher corrosion protection than high-quality Alkaliphos- phosphate coatings.
- the object is achieved by a method for coating metallic surfaces with an acidic aqueous conversion composition, which is a solution or dispersion characterized in that it contains:
- particulate SiO 2 having an average particle diameter ⁇ 0.3 ⁇ m, measured on a scanning electron microscope and based on the solids content
- the content of molybdate is calculated as MoO 4 2+ or / and the content of P-containing oxyanions calculated as PO 4 3+ is in each case ⁇ 0.1 g / L or approximately 0 g / L and wherein the acidic aqueous composition has a pH in the range of 2.5 to 6.5, and preferably in the range of 3.0 to 5.5.
- the ions of TiF 6 2+ , ZrF 6 2+ or / and HfF 6 2+ are largely equivalent and interchangeable in the acidic aqueous conversion composition, but in many cases the ions of ZrF 6 2+ give the best properties of the conversion coating produced herewith.
- the content of the acidic aqueous conversion composition of TiF 6 2+ , ZrF 6 2+ or / and HfF 6 2+ is 0.05 to ⁇ 1 g / L, 0.1 to 0.8 g / L, 0.15 to 0.50 g / L or 0.20 to 0.33 g / L.
- a cation content of the aqueous acidic composition only conversion of Fe 2+ ions, based on the total content of Fe 2+ - at least partially derived, Mn and Zn ions, this content from a deliberate addition.
- the ions of manganese and zinc, and to a limited extent Fe 2+, are largely equivalent and interchangeable in the acidic aqueous conversion composition, but many times the ions of manganese and / or zinc give the best properties of the conversion coating produced therewith.
- manganese and zinc are added to the acidic conversion aqueous composition, it is particularly preferable to obtain a manganese content higher than the zinc content.
- It preferably contains 0 or 0.01 to 0.3 g / L or 0.02 to 0.15 g / L of Fe 2+ ions and 0.01 to 1 g / L of Mn ions and / or 0, 01 to 1 g / L or 0.1 to 0.6 g / L of Zn ions. More preferably, it contains 0.1 to 0.6 g / L or 0.2 to 0.4 g / L of Mn ions and / or 0.1 to 0.6 g / L or 0.2 to 0.4 g / L of Zn ions.
- phosphate-free ⁇ 0.1 g / L PO 4
- completely phosphate-free about 0 or exactly 0 g / L PO 4
- a content of phosphate calculated as PO 4 3+ between 0.001 and ⁇ 0.1 g / L can not be excluded, in particular due to entrainment and impurities.
- organic polymer or / and organic copolymer can contribute to the fact that the properties of the conversion coating produced herewith can be further improved and that, if necessary, a subsequent coating can be dispensed with.
- the content of the acidic organic polymer or / and organic copolymer conversion composition is 0.01 to 3 g / L, 0.1 to 2.5 g / L, 0.2 to 2 g / L, 0.4 to 1, 5 g / L or 0.6 to 1, 2 g / L.
- the organic polymer and / or copolymer is preferably one based on (meth) acrylate / (meth) acrylic acid and / or vinyl acetate-acrylic copolymer. In the absence of a coating, it is possible to speak of passivation layer in the coating produced and of blank corrosion protection in the case of corrosion protection.
- ultrafine particulate SiO 2 (in particular ⁇ 0.3 ⁇ m), for example SiO 2 nanoparticles, can show a similar positive effect as an addition of organic polymer or / and organic copolymer, but often with the difference that the layer formation and thus the coating is even more uniform with SiO 2 .
- At least one nonionic, anionic, cationic or / and zwitterionic surfactant can be added.
- An addition of at least one nonionic surfactant is particularly preferred here.
- an addition of anions selected from the group consisting of carbonate, nitrate and sulfate often takes place via the addition of cations via water-soluble salts.
- nitrates are particularly preferred.
- carboxylate anions for example via acetic acid or / and via a manganese carboxylate
- carboxylate anions for example via acetic acid or / and via a manganese carboxylate
- carboxylic acids and their derivatives such as salts and esters, which are water-soluble, can be added are stable to the pH range, which do not have a complicated composition of matter which form anions in water which, depending on the nature and amount of the anions, do not impair the film formation and which, if appropriate, complex alkali or / and alkaline earth metal ions which do not participate in the film formation.
- aliphatic carboxylic acids and mono-, di- and / or polycarboxylic acids such as hydroxycarboxylic acids.
- carboxylate anions care must be taken to ensure that they do not impair the formation of layers, since, for example, citrate and some other complexing agents may, depending on the type and amount of anions, impair the layer formation.
- an addition of at least one sulfonic acid such as, for example, methanesulfonic acid, amidosulfonic acid or / and one of its derivatives may be advantageous in order to act as an accelerator and / or as a further counterion.
- a content of molybdate is calculated as MoO 4 of 0 or in the range of 0.01 to ⁇ 0.5 g / L, in particular from 0.02 to 0.3 or g / L, from 0.01 to ⁇ 0, 1 g / L preferred.
- An addition of molybdate has proven itself only at very low addition levels.
- P-containing oxyanions e.g. Orthophosphate, condensed phosphates and phosphonates
- P-containing oxyanions e.g. Orthophosphate, condensed phosphates and phosphonates
- P-containing oxyanions it is preferred for reasons of environmental compatibility and the avoidance of disposal that no content of P-containing oxyanions is added, and it is preferably to ensure that as far as possible no content of P-containing oxyanions is introduced ,
- the acidic aqueous composition optionally additionally contains, consists essentially of or consists of: 0.03 to 5 g / L of the sum of ions of lithium, sodium and / or potassium, 0 or 0.05 to 5 g / L of ammonium ions,
- levels of lithium, sodium, potassium or / and ammonium are usually unavoidable in order to achieve charge balance and to control not only multivalent cations, e.g. Add heavy metal ions.
- monovalent cations sodium ions are particularly preferred. They are largely equivalent and interchangeable in the acidic aqueous conversion composition and often necessary for pH regulation.
- An addition to at least one accelerator is sometimes beneficial, in particular an addition of a chlorate, nitrite or / and peroxide. In this case, however, to pay attention to the appropriate amount, for example, to a content of NO 2 of significantly less than 1 g / L.
- the layer formation can be accelerated and the properties of the coating produced thereby improved.
- an overdose of accelerator should be avoided in order not to impair the film formation as in Example B40. Addition of nitroguanidine has not proved beneficial.
- At least one vanadium compound can significantly increase the corrosion protection.
- further elemental contents of the metallic surfaces of the substrates and of the systems can be introduced into the bath by pickling of the acidic aqueous conversion composition and optionally also accumulate in the bath composition, in particular Fe 2+ ions and alloying elements or their ions.
- levels of ions and substances from other plant areas for example from a previously used purification step, may be introduced in small quantities despite rinsing with water.
- contents of alkali metals, ammonium, complexing agents, surfactants, anionic impurities of the cleaning bath or / and further impurities or of their ions can be introduced into the bath composition according to the invention.
- a separate preceding purification step is not necessarily provided, so that foreign ion input by a chemical treatment solution can be largely excluded.
- a cleaning step can be carried out with surfactant-containing water and without a scaffold (builder).
- the cleaning may be carried out before the conversion coating so that it is cleaned before contacting the substrate with the aqueous composition, in particular with an alkaline cleaning.
- the aqueous composition may also contain at least one surfactant, so that the cleaning and conversion coating takes place (also) in the same process step.
- the aqueous conversion composition preferably contains no content or only a low content, such as in each case up to 0.1 g / L of carboxylic acids, phosphates, phosphonates or / and of compounds and / or ions of calcium, chromium, chromate, cobalt, copper, Magnesium, molybdenum, nickel, vanadium or / and tin and / or of silane / silanol / siloxane / polysiloxane deliberately added.
- a low content such as in each case up to 0.1 g / L of carboxylic acids, phosphates, phosphonates or / and of compounds and / or ions of calcium, chromium, chromate, cobalt, copper, Magnesium, molybdenum, nickel, vanadium or / and tin and / or of silane / silanol / siloxane / polysiloxane deliberately added.
- Silane / silanol / siloxane / polysiloxane means silane, silanol, siloxane or / and polysiloxane, because in water and in coating, for example starting from a silane, silanols or / and siloxanes can very quickly result, which sometimes also - depending on the chemical definition - Can give polysiloxanes.
- the content of the acidic aqueous conversion composition of alkaline earth metals such as calcium or / and magnesium is preferably not higher than 0.2 g / L together to avoid precipitation in the presence of fluorides as much as possible.
- the acidic aqueous conversion composition has a pH in the range of 2.5 to 6.5 and contains, consists essentially of or consists of:
- each of Fe 2+ , Mn and / or Zn ions of which at least one kind of these ions in the content range of 0.01 to 1 g / L is contained, and optionally 0 , 01 to 2 g / L of particulate SiO 2 with a mean particle diameter diameter ⁇ 0.3 ⁇ , based on the solids content and / or
- each of Fe 2+ , Mn and / or Zn ions of which at least one kind of these ions is contained in the content range of 0.01 to 1 g / L, and 0, 01 to 2 g / L of organic polymer and / or copolymer which is stable at a pH ⁇ 6.5, based on the solids content,
- particulate SiO 2 having a mean particle diameter ⁇ 0.3 ⁇ m, based on the solids content
- a content of molybdate calculated as MoO 4 2+ or / and a content of P-containing oxyanions calculated as PO 4 3+ is in each case ⁇ 0.1 g / L or about 0 g / L.
- each of Fe 2+ , Mn and / or Zn ions of which at least one kind of these ions is contained in the content range of 0.01 to 1 g / L, and a content calculated on molybdate as MoO 4 2+ in the range of 0.01 to ⁇ 0.5 g / L and optionally 0.01 to 2 g / L of organic polymer and / or copolymer, which at a pH ⁇ 6.5 is stable, based on the solids content,
- a content of molybdate calculated as MoO 4 2+ in the range of 0.01 to ⁇ 0.5 g / L and a content of P-containing oxyanions calculated as PO 4 3+ ⁇ 0.1 g / L or about 0 g / L is.
- Mn and / or Zn ions are added, while the content of Fe 2+ ions is preferably leached out of the iron-rich metallic substrate only by a pickling effect of the acidic conversion composition. If necessary, the coating is then painted at least once.
- an acidic aqueous conversion composition that is a solution or dispersion that contains, consists essentially of or consists of:
- Type of these ions is contained in the content range of 0.01 to 1 g / L,
- particulate SiO 2 having an average particle diameter ⁇ 0.3 ⁇ m, measured on a scanning electron microscope and based on the solids content
- the content of molybdate is calculated as MoO 4 2+ or / and the content of P-containing oxyanions calculated as PO 4 3+ is in each case ⁇ 0.1 g / L or approximately 0 g / L and wherein the aqueous composition has a pH Value in the range of 2.5 to 6.5, and preferably in the range of 3.0 to 5.5.
- the acidic aqueous composition contains, consists essentially of or additionally consists of:
- the bath composition according to the invention may preferably be prepared by diluting one or two concentrates with water by a dilution factor in the range from 5: 1 to 40: 1.
- the second concentrate could, for example, contain at least one surfactant and also be aqueous.
- Fluoride can also be added as monofluoride, as bifluoride or / and in the form of the corresponding acids.
- the content of free fluoride is often in the range of 0.01 to 0.2 g / L.
- the acidic aqueous conversion composition is worked with city water having a conductance of, for example, about 200 to 600 S / cm, or with demineralized water, both for the makeup and for supplementing the liquid level in the bath, as well as for the first rinse the conversion coating.
- a demineralised water rinse with demineralized water is only required as a final rinse by default, to prevent the salt load from drying up, which can lead to inferior corrosion protection.
- HDG hot-dip galvanized sheet steel
- CRS cold rolled steel
- the properties of the coating on hot-dip galvanized steel sheets are often improved.
- a content of Fe 2+ ions often does not deteriorate the properties of the coating, but it turns out that Fe 2+ ions are gradually oxidized to Fe 3+ and settle as bath sludge. Therefore, it is preferred that the acidic aqueous conversion composition has a content of manganese and / or zinc ions.
- a surfactant-containing aqueous composition may help to further improve cleaning either after degreasing and / or pickling, or at least to dispense with degreasing prior to conversion coating so that one-pot operation can be carried out to remove and eliminate the cleaning step Frame of the conversion coating takes place.
- At least one substrate having metallic surfaces be contacted with the aqueous composition for a time in the range of 1 second to 10 minutes, more preferably 0.5 to 10 minutes in the treatment of parts.
- it is particularly preferably brought into contact for a period of time in the range from 1 to 10 minutes, in particular during dipping or, preferably, from 0.5 to 6 minutes, in particular during spraying.
- the same treatment times as in Alkaliphosphatieren can be used in these compositions, which means a switch from systems of an alkali phosphating on the inventive Conversion coating facilitates. Because alkaline phosphating often takes 3 to 5 minutes.
- composition according to the invention can also be applied to tape, if rinsing is still carried out with water after the band coating (rinse method).
- the metallic tape is preferably contacted with the aqueous composition for a time in the range of 1 second to 2 minutes.
- the substrate having metallic surfaces when in contact with the aqueous composition has a temperature in the range of 5 to 90 ° C and preferably in the range of 15 to 70 ° C or 30 to 60 ° C.
- the aqueous composition has a temperature in the range of 35 to 70 ° C or 45 to 60 ° C when contacted with the metallic surface substrate.
- the object is also achieved with a coated substrate with metallic surfaces, which has been coated according to the invention.
- the coating produced thereby has a layer thickness of 0.3 to 3 ⁇ m and / or that the sum of the coating of elementarily measured zirconium and / or titanium in the conversion coating is in the range from 1 to 300 mg / m 2 or preferably in the range of 15 to 150 mg / m 2 , measured with an X-ray fluorescence system (RFA).
- RFA X-ray fluorescence system
- the coating produced hereby is colored, iridescent or gray.
- interference colors of FIG. 1 occur. or a higher order or colors where the interference color is superimposed with the color of ions. These colours are similar or similar to an alkali phosphate coating. The colors often help to approximate the thickness and in part the uniformity and / or quality of a coating. If this is possible even with a larger viewing distance, this is particularly advantageous in a coating process.
- the conversion coating according to the invention produced therewith is subsequently rinsed with water or with an aqueous rinsing solution, in particular with a content of silane, organic polymer or / and organic copolymer, and optionally also varnished.
- aqueous rinse solutions such as with Gardolene ® D95 with a content of phenolic resin, or with Gardolene ® D6890 based on silane.
- the aqueous rinsing solution particularly preferably contains a content of at least one a) cation selected from alkaline earth metal, aluminum, titanium, yttrium and heavy metal cations, b) organic polymer or / and copolymer, c) silane, silanol, siloxane or / and Polysiloxane and / or d) complex fluoride, wherein complex fluoride is also the corresponding fluorine-containing acid.
- Particularly preferred silanes here are aminosilanes having one, two or even more amino groups and / or bis-silyl silanes.
- a coating is applied with an aqueous acidic composition according to the invention, optionally followed by rinsing with water and / or rinsing with an aqueous composition, if appropriate, and then the at least one coating produced in this way is subsequently painted at least once.
- aqueous acidic composition based on from 0.01 to 1 g / L of TiF 6 2+ , ZrF 6 2+ or / and HfF 6 2+ or only ZrF 6 2+ in Form of lo- calculated as ZrF 6 2+ and 0 or 0.01 to 1 g / L each of Fe 2+ , Mn and / or Zn ions, of which at least one kind of these ions in the content range of 0.01 to 1 g / L is contained, and optionally 0.01 to 2 g / L of particulate SiO 2 having an average particle diameter ⁇ 0.3 ⁇ , based on the solids content and / or optionally 0.01 to 10 g / L of at least one surfactant, which is essentially phosphate-free and substantially phosphonate-free, a coating is applied, if appropriate subsequently rinsed with water and / or optionally thereafter with an aqueous composition based on zirconium
- a surfactant content in the aqueous acidic composition according to the invention may optionally be dispensed with a prior purification stage.
- the conversion coating according to the invention produced herewith if it contains no organic polymer and no organic copolymer, can preferably be dried without subsequent rinsing with water or preferably with an aqueous rinsing solution, in particular containing silane, organic polymer or / and organic copolymer, and optionally also to be painted.
- the conversion coating according to the invention produced herewith may alternatively, if it contains organic polymer and / or copolymer, preferably be used without a coating with a primer, lacquer or adhesive.
- the conversion coating produced hereby according to the invention may, if appropriate after at least one rinse with water and / or with an aqueous rinsing solution, be coated at least once with a primer, lacquer or adhesive.
- the coating produced hereby can excellently provide a replacement for an alkali phosphate coating such as e.g. represent an iron phosphate coating.
- the at least one substrate with metallic surfaces which has been coated according to the invention is preferably used as an architectural element, as a container, as a construction or connection element, as a profile element, as a radiator element, as a more complicated molded part or / and as a component in construction, energy technology, vehicle construction , Appliances, Home Appliances or Mechanical Engineering.
- composition according to the invention and the process according to the invention are particularly advantageous in the chemical pretreatment of surfaces of various steel substrates used in the metalworking industry. find a turn. This can even be cleaned in one step and at the same time a coatable conversion layer can be applied, to which this three-stage treatment method from cleaning with conversion coating, flushing with city water and rinsing with fully desalinated water is completely sufficient. Especially the bath analysis is very easy to handle, since a precise determination of the anions and cations is rarely necessary, since the pH value and the conductivity provide sufficient information on the chemical bath state.
- the process according to the invention can be used to produce a colored, iridescent, gray or colorless (as in B40) passivation layer (without coating) or a colored, iridescent, gray or colorless (as in B40) conversion coating (with coating).
- a passivation layer is also a conversion-produced coating. Therefore, the term "conversion coating” in the context of this application also includes the term “passivation layer” as long as or when no coating is applied, e.g. even with the claims.
- the process according to the invention can be used as a replacement for an alkali phosphating process or even as a substitute for a zinc phosphating process.
- the products produced by the process according to the invention can be used in a variety of ways, in particular as an architectural element, as a container, as a construction or connecting element, as a profile element, as a radiator element, as a more complicated molded part or / and as a component in construction, power engineering, vehicle construction , Appliances, household appliances or mechanical engineering and, for example, as a radiator, as racks, as plates, as panels, as angles or as components in the vehicle or aircraft interior.
- Aqueous conversion compositions according to Table 1 were prepared.
- the surfactant used was a nonionic surfactant Gardobond ® Additive H7438, which provided additional cleaning of the metal surface.
- the alkaline, with potassium hydroxide stabilized SiO 2 dispersion Gardobond ® additive H 7157 Chemetall GmbH had a solids content of 20% and an average particle size of 0.2 ⁇ .
- the polymer dispersion 1 AC 2773 based on acrylate from Alberdingk had a solids content of 53%.
- the acrylate-containing copolymer dispersion 2 VA 294 VP from Alberdingk had a solids content of 47%.
- the acrylate-containing copolymer dispersion 3 AS 2084 VP from Alberdingk had a solids content of 53% solids.
- Polymer, copolymer, SiO 2 particles and / or surfactant were added to the previously prepared aqueous conversion composition separately at the end of the mixing operation. In individual experiments, ammonium molybdate was added.
- a lacquer layer on the conversion-coated panels was thereafter each applied: either an epoxy polyester powder coating Interpon ® 700 from Akzo Nobel Powder Coatings GmbH ⁇ in a layer thickness of 60 to 80, a wet paint Alexit ® monolayer on the basis of polyurethane and isocyanate of Mankiewicz in a layer thickness of 60 to 80 ⁇ or a black cathodic dip coating Cathoguard ® 350 BASF in a layer thickness of 15 to 20 ⁇ in Example B3 or in Examples B45 to B48 cathodic dip coating Cathoguard ® 800 (KTL) from BASF in one Layer thickness of 15 to 20 ⁇ and then each one layer of a car body after Daimler Benz from 25-30 ⁇ filler, 1 1 -15 ⁇ basecoat and 40-50 ⁇ clearcoat.
- Interpon ® 700 from Akzo Nobel Powder Coatings GmbH ⁇ in a layer thickness of 60 to 80
- a wet paint Alexit ® monolayer on the basis of polyurethane and is
- the paint adhesion of the painted samples was determined in the cross-hatching method in accordance with DIN EN ISO 2409 before or after 240 h of a change in climate change.
- the corrosion resistance of the painted samples was determined in the salt spray test according to DIN 50021 for 500 hours in the neutral salt spray test NSS. Unlike in the Asian and North American market, only a single layer of varnish was applied.
- Table 1 Overview of the compositions of the aqueous baths and the properties of the associated coated samples and coatings
- the aqueous conversion compositions according to the invention give excellent coatings which have excellent corrosion resistance under these conditions, excellent paint adhesion and, in most cases, a clear color. Both strongly colored and colorless coatings can be produced with these compositions.
- the corrosion resistance on steel surfaces is almost as good as that of high grade zinc phosphating and thus far superior to high corrosion alkali phosphating (e.g., B3 vs. VB1).
- the coating properties were determined only after an additional second conversion treatment-unlike the examples according to the invention.
- the paint adhesion on steel surfaces is even as good as that of a high-quality zinc phosphating and thus the paint adhesion of a high-quality alkali phosphating very clearly superior.
- the aqueous conversion compositions according to the invention are composed quite environmentally friendly, work-hygiene advantageous and phosphate-free.
- a rinse solution e.g. was used with a content of silane, organic polymer and / or organic copolymer after the conversion coating according to the invention and after at least one rinsing with water, a paint adhesion was achieved on steel surfaces, which is at least as good as that of a high-quality zinc phosphating, and was achieves corrosion resistance at least as good as zinc phosphating.
- the acidic aqueous conversion compositions according to the invention are outstandingly suitable for the replacement of alkali phosphating on various metallic substrate surfaces and not only for iron phosphating on iron and steel surfaces. This has even resulted in a multimetal ability in the treatment, so that a mix of different types of metallic surfaces in the same bath can be treated simultaneously or successively.
- Fe 2+ can be replenished from the substrate by a reaction-related pickling process from the bath of iron-containing substrate surfaces. However, this is then often oxidized by the Badumicalzung to Fe 3+ and removed from the bath as a reactive constituent. Despite the addition of Fe 2+ , a steady state Fe 2+ concentration frequently occurs in the range of 0.025 to 0.1 g / L Fe 2+ , as in Examples B41 and B42.
- the main elements and a part of the alloying elements are leached out in the acidic aqueous conversion composition and can partially accumulate in the bath composition, then it is common for a plurality of cations to be present in the bath at the same time to the cooperation composition of the coating and subordinate to their properties.
- Zn and Mn are deposited only in non-measurable quantities based on measurements with X-ray fluorescence analysis.
- Zr is the main constituent of the layer and may be present as (Zr (OH) x F y ), for example.
- Zn often acts as a fluoride scavenger in the metal-cladding interface, allowing less fluoride to be incorporated into the layer, which Applicant understands to give better results.
- Zn and Mn are only minor constituents of the layer and can therefore be detected more accurately analytically only by XPS / ESCA photoelectron spectroscopy.
- the produced properties of the coatings are often best when the Zr support is highest in comparable experiments.
- the Zr overlay is different for different steel grades and also for the same steel grade with different surface properties.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102014201209 | 2014-01-23 | ||
PCT/EP2015/051272 WO2015110541A1 (en) | 2014-01-23 | 2015-01-22 | Method for coating metal surfaces, substrates coated in this way, and use thereof |
Publications (2)
Publication Number | Publication Date |
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EP3097221A1 true EP3097221A1 (en) | 2016-11-30 |
EP3097221B1 EP3097221B1 (en) | 2022-05-04 |
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ID=52462284
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EP15703001.6A Active EP3097221B1 (en) | 2014-01-23 | 2015-01-22 | Method for coating metal surfaces, substrates coated in this way, and use thereof |
Country Status (15)
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US (1) | US20170009351A1 (en) |
EP (1) | EP3097221B1 (en) |
JP (1) | JP6622206B2 (en) |
KR (1) | KR102416141B1 (en) |
CN (1) | CN106574372B (en) |
AU (1) | AU2015208176B2 (en) |
BR (1) | BR112016017018B1 (en) |
CA (1) | CA2938414A1 (en) |
DE (1) | DE102015201090A1 (en) |
ES (1) | ES2921449T3 (en) |
HU (1) | HUE059458T2 (en) |
PL (1) | PL3097221T3 (en) |
RU (1) | RU2691149C2 (en) |
WO (1) | WO2015110541A1 (en) |
ZA (1) | ZA201605375B (en) |
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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 |
EP3659716A1 (en) * | 2018-11-27 | 2020-06-03 | Rhodia Operations | Polymers for metal surface treatment |
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US20110111235A1 (en) * | 2004-11-10 | 2011-05-12 | Thomas Kolberg | Process for coating metallic surfaces with a multicomponent aqueous composition |
US20110189488A1 (en) * | 2005-04-04 | 2011-08-04 | Thomas Kolberg | Process for coating metallic surfaces with an aqueous composition, and this composition |
WO2014137796A1 (en) * | 2013-03-06 | 2014-09-12 | Ppg Industries Ohio, Inc. | Methods for treating a ferrous metal substrate |
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2015
- 2015-01-22 WO PCT/EP2015/051272 patent/WO2015110541A1/en active Application Filing
- 2015-01-22 PL PL15703001.6T patent/PL3097221T3/en unknown
- 2015-01-22 KR KR1020167022936A patent/KR102416141B1/en active IP Right Grant
- 2015-01-22 EP EP15703001.6A patent/EP3097221B1/en active Active
- 2015-01-22 HU HUE15703001A patent/HUE059458T2/en unknown
- 2015-01-22 CN CN201580015618.8A patent/CN106574372B/en active Active
- 2015-01-22 CA CA2938414A patent/CA2938414A1/en not_active Abandoned
- 2015-01-22 US US15/113,489 patent/US20170009351A1/en not_active Abandoned
- 2015-01-22 DE DE102015201090.2A patent/DE102015201090A1/en not_active Withdrawn
- 2015-01-22 RU RU2016134227A patent/RU2691149C2/en active
- 2015-01-22 BR BR112016017018-0A patent/BR112016017018B1/en active IP Right Grant
- 2015-01-22 JP JP2016548170A patent/JP6622206B2/en active Active
- 2015-01-22 AU AU2015208176A patent/AU2015208176B2/en active Active
- 2015-01-22 ES ES15703001T patent/ES2921449T3/en active Active
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2016
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WO2005042801A1 (en) * | 2003-10-23 | 2005-05-12 | Basf Aktiengesellschaft | Essentially chromium-free method for passivating metallic surfaces consisting of zn, zn alloys, al or al alloys |
US20110111235A1 (en) * | 2004-11-10 | 2011-05-12 | Thomas Kolberg | Process for coating metallic surfaces with a multicomponent aqueous composition |
US20110189488A1 (en) * | 2005-04-04 | 2011-08-04 | Thomas Kolberg | Process for coating metallic surfaces with an aqueous composition, and this composition |
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Also Published As
Publication number | Publication date |
---|---|
US20170009351A1 (en) | 2017-01-12 |
KR102416141B1 (en) | 2022-07-04 |
KR20160111989A (en) | 2016-09-27 |
WO2015110541A1 (en) | 2015-07-30 |
ZA201605375B (en) | 2017-11-29 |
AU2015208176B2 (en) | 2018-11-08 |
ES2921449T3 (en) | 2022-08-25 |
BR112016017018B1 (en) | 2022-09-06 |
PL3097221T3 (en) | 2022-08-29 |
DE102015201090A1 (en) | 2015-07-23 |
JP6622206B2 (en) | 2019-12-18 |
CN106574372B (en) | 2020-11-24 |
JP2017506291A (en) | 2017-03-02 |
AU2015208176A1 (en) | 2016-08-25 |
RU2016134227A (en) | 2018-03-01 |
RU2691149C2 (en) | 2019-06-11 |
CN106574372A (en) | 2017-04-19 |
CA2938414A1 (en) | 2015-07-30 |
RU2016134227A3 (en) | 2018-11-08 |
HUE059458T2 (en) | 2022-11-28 |
BR112016017018A2 (en) | 2017-08-08 |
EP3097221B1 (en) | 2022-05-04 |
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