EP0134895B1 - Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques - Google Patents
Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques Download PDFInfo
- Publication number
- EP0134895B1 EP0134895B1 EP84105731A EP84105731A EP0134895B1 EP 0134895 B1 EP0134895 B1 EP 0134895B1 EP 84105731 A EP84105731 A EP 84105731A EP 84105731 A EP84105731 A EP 84105731A EP 0134895 B1 EP0134895 B1 EP 0134895B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- phosphate
- layer
- compounds
- accelerating
- 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.)
- Expired
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 46
- 239000010452 phosphate Substances 0.000 title claims description 46
- 150000001875 compounds Chemical class 0.000 title claims description 26
- 238000000576 coating method Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 13
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 claims description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 3
- OSKILZSXDKESQH-UHFFFAOYSA-K zinc;iron(2+);phosphate Chemical compound [Fe+2].[Zn+2].[O-]P([O-])([O-])=O OSKILZSXDKESQH-UHFFFAOYSA-K 0.000 claims description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- SPEBLRRMVBYHLS-UHFFFAOYSA-N oxathiazin-4-one;potassium Chemical compound [K].O=C1NSOC=C1 SPEBLRRMVBYHLS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229940124530 sulfonamide Drugs 0.000 abstract description 3
- 150000003456 sulfonamides Chemical class 0.000 abstract description 3
- JELWTDFYWODDQR-UHFFFAOYSA-N oxathiazin-4-one Chemical class O=C1NSOC=C1 JELWTDFYWODDQR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 238000007746 phosphate conversion coating Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 94
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 56
- 239000010410 layer Substances 0.000 description 45
- 235000021317 phosphate Nutrition 0.000 description 45
- 239000012141 concentrate Substances 0.000 description 41
- 238000011282 treatment Methods 0.000 description 38
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 34
- 239000002253 acid Substances 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 26
- 239000011701 zinc Substances 0.000 description 22
- 229910052725 zinc Inorganic materials 0.000 description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 18
- 238000005507 spraying Methods 0.000 description 17
- 238000004448 titration Methods 0.000 description 17
- 241001295925 Gegenes Species 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 14
- 239000003973 paint Substances 0.000 description 14
- 239000007921 spray Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- -1 aromatic nitro compound Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 150000003608 titanium Chemical class 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 6
- 230000009189 diving Effects 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 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 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- AAQCEEMRPKWTMP-UHFFFAOYSA-N [Br].CC1=CC=CC=C1O Chemical compound [Br].CC1=CC=CC=C1O AAQCEEMRPKWTMP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000000126 substance 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical class OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229940077464 ammonium ion Drugs 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
- 238000003618 dip coating Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940045845 sodium myristate Drugs 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N C1CC=CCC1 Chemical compound C1CC=CCC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- SWCXDRFQESAGQM-UHFFFAOYSA-N CCCCCCCNCC(CCC1S(C)=O)CC1C(NC)=O Chemical compound CCCCCCCNCC(CCC1S(C)=O)CC1C(NC)=O SWCXDRFQESAGQM-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229960001479 tosylchloramide sodium Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc 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
- C23C22/05—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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
-
- 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
- C23C22/42—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 phosphates
Definitions
- DE-A-30 16576 describes a method for accelerating the formation of phosphate layers based on zinc phosphate, the application solution containing nitrite and chlorate as accelerators.
- a method based on a solution of zinc phosphate uses a combination of chlorate and a water-soluble aromatic nitro compound, preferably Na-m-nitrobenzenesulfonate (DE-A-32 24 923) as accelerator.
- a comparable combination is claimed in GB-A-15 42 222.
- DE-A-30 04 927 also describes a method for forming phosphate layers on metal surfaces with the aid of zinc phosphate solutions which contain nitrite and / or organic nitro compounds and, if appropriate, additionally chlorate.
- US-A-3 923 554 relates to a method for producing phosphate layers on iron surfaces with the aid of aqueous zinc phosphate solutions which contain nitrite ions.
- aqueous zinc phosphate solutions which contain nitrite ions.
- 0.1 to 10 g / l, based on the total solution, of urea or urea nitrate are added to these solutions.
- the same effect can also be achieved by adding sulfamic acid, alkali metal or ammonium salts of sulfamic acid, ascorbic acid, hydroxylamine or hydroxylamine derivatives to such solutions.
- the appearance and the corrosion resistance of the layers are not impaired by the additives mentioned, but rather improved.
- NL-C-102 953 is a phosphating process in which phosphating solutions are used which, in addition to chlorate and / or nitrate or nitrite or halogenate, are also a compound of the general formula RS0 2 NHCI, in which R is an aralkyl radical with at most 5 carbon atoms in the alkyl chain, contained as accelerators.
- phosphating solutions which, in addition to chlorate and / or nitrate or nitrite or halogenate, are also a compound of the general formula RS0 2 NHCI, in which R is an aralkyl radical with at most 5 carbon atoms in the alkyl chain, contained as accelerators.
- their salts such as in particular chloramine-T, can also be used.
- phosphating solutions often contain nitrate. Carrying out the phosphating process at elevated temperature in the presence of nitrates increasingly leads to an autoreduction of the nitrate with the formation of additional nitrite. The formation of these amounts of nitrite is difficult to control and is undesirable since - as mentioned above - there is an increasing passivation of the metal surfaces.
- a particular disadvantage is that the use of nitrite-containing systems to accelerate phosphating solutions leads to the release of nitrous gases. This disadvantage makes it seem advisable to completely dispense with the use of nitrite and possibly nitrate as a phosphating accelerator or to choose reaction conditions under which nitrite does not form.
- the adjustment and maintenance of the pH value is of great importance for the formation of a good phosphate layer.
- the pH can be between 1.8 and 5.8. It is preferably adjusted to the desired value using phosphoric acid.
- sulfamic acid is also described for this purpose.
- the subject of DE-A-21 52 446 - or the parallel FR-A-21 10784 and BE-A-767 775 - is, for example, a process for phosphating metal surfaces with the aid of aqueous solutions which contain acidic non-layer-forming phosphates.
- sulfamic acid is used as the acidic component for adjusting or maintaining the pH in amounts of 0.5 to 10% by weight, preferably 3 to 6% by weight, based on the content of acidic non-layer-forming phosphate in the solution.
- such solutions contain oxidizing accelerators, such as nitrates, nitrites, chlorates or molybdates.
- phosphate coatings For corrosion protection and as a lubricant carrier in cold forming, thick and fully developed phosphate coatings with coating weights of 10 to 35 g / m 2 are desirable. Such high contact weights are normally achieved at phosphating bath temperatures of 70 to 100 ° C.
- DE-A-22 41 798 describes such a nitrate-accelerated immersion process in which the weight ratio of P 2 0 5 : Zn: N0 3 is 1: (0.7 to 2.0): (0.3 to 0.7) must be set.
- DE-C-15 21f927 also claims a nitrate-accelerated process in which the weight ratio P 2 O 5 : Zn: N0 3 should be 1: (1.4 to 2.6): (2.0 to 4.3) .
- soaps in combination with phosphate layers are used as lubricants.
- the zinc phosphate layers on the workpiece can partially do so with alkali soaps be implemented so that the particularly effective zinc soap is formed.
- the tertiary zinc phosphate of the layer reacts with sodium soap to form zinc soap and tertiary sodium phosphate.
- the phosphated workpieces are immersed in a soaping bath at 70 to 80 ° C. for 2 to 10 minutes. The greatest possible conversion and thus the best forming results are obtained with special reactive soap lubricants, the immersion baths used with 2 to 10% by weight of which have a pH between 8 and 1-0.
- the formation of the phosphate layers can be influenced by special pre-rinses. With such pre-rinses, it is often possible to exaggerate the effects of previous treatments, e.g. B. an alkaline degreasing or pickling. Such pre-rinses are therefore widely used in practice.
- Zinc phosphating processes based on the so-called low zinc technology are also used. This is a process variant that differs from normal zinc technology in some essential points. These variants concern in particular the concentrations in which the determining bath components zinc and phosphate are present in the treatment solution and the weight and molar ratios of these two components to one another. While the weight ratio of zinc to phosphate is about 1: (1 to 12) in the normal zinc phosphating baths, with which metal surfaces are treated for subsequent painting, it is 1: (14 to 30) in the low zinc phosphating baths.
- the monitoring of the phosphating baths is relatively complex, especially since the ratio of chemical consumption to mechanical discharge, which in turn u. a. depends on the shape of the metal piece being treated, on the draining options and on the type of phosphating system, is not a constant.
- the object of the present invention is to provide a method for accelerated and layer-improving application of phosphate coatings on metal surfaces which does not have the aforementioned disadvantages.
- a process should be made available that does not require nitrite as an accelerator component and also leads to the same results in terms of paint adhesion and corrosion protection in normal zinc technology that can be achieved with low zinc technology.
- simplifying the monitoring of the contents of the individual accelerator components was intended to simplify bath management and reduce the amount of sludge in the phosphating baths.
- the new process should also be based on the use of environmentally friendly and toxicologically safe compounds.
- N-substitution products of amidosulfonic acid also called sulfamic acid
- salts generally formula 1
- sulfonamides generally formula I
- benzenesulfanilides generally formula
- Benzoeklaresulfimide generally formula
- 1,2.3-oxathiazin-4 (3H) -one salts and their 6-alkyl derivatives (general formula 111) used individually or in combination with one another in addition to other components commonly used in phosphating solutions.
- the invention accordingly relates to the use of one or more compounds of the general formulas (I), (II) and (111) defined above as accelerating and layer-refining components, in an amount of 0.1 to 6 g / l, in phosphating solutions on the Basis of zinc phosphate and / or iron phosphate and / or zinc iron phosphate, which are used to apply phosphate coatings on metal surfaces, in addition to other components that are commonly used in such phosphating solutions.
- the compounds of the general formulas (I), (11) and (III) according to the invention are used in combination with m-nitrobenzenesulfonic acid as a co-accelerator. This leads to an effective acceleration of the phosphating process.
- nitrate and - in the presence of compounds of the general formulas (III) - nitrite can also be used as co-accelerators.
- one or more compounds from the group N-cyclohexanesulfamic acid and its salts, benzenesulfanilide, benzoic acid sulfimide, 1,2.3-oxathiazin-4 (3H) -one potassium and its 6-methyl derivative are used as accelerating and layer-refining components used.
- Other sulfonamides are also suitable, in particular those whose aromatic radical carries further polar radicals which improve the water solubility of the compounds, such as, for. B. hydroxy or amino residues or amido residues of dicarboxylic acids.
- the water solubility of the compounds according to the invention should be so good. that at least Dissolve 2 g of the compounds of the general formulas (I), (11) and / or (111) in one liter of phosphating solution.
- water-soluble salts preferably alkali metal salts of the N-substituted derivatives of amidosulfonic acid, and / or further compounds are selected which carry polar groups which improve water solubility as substituents.
- the active constituents of the phosphating solution can be introduced into water in the form of water-soluble or acid-soluble salts or compounds or as acids in a manner known per se.
- the presence of chlorate is not absolutely necessary for the formation of phosphate layers. Rather, phosphate layers with high coating weights are formed by the process accelerated according to the invention in the presence and in the absence of chlorate. In the absence of chlorate, small additions of molybdate can also be used.
- Optimal phosphate layer formation for subsequent coating with paints and other organic coatings with regard to paint adhesion and corrosion is obtained if chlorate is used as a further accelerator component in accordance with a preferred embodiment of the present invention and the ratio of the compounds of the general formulas (I), ( 11) and / or (111) for C10 3 to a value in the range from (0.1 to 10): 1.
- a further preferred embodiment of the invention leads to optimal phosphate layer formation if the ratio of the compounds of the general formulas (I), (11) and / or (111) according to the invention to Mo0 4 is set to a value in the range of (10 to 100): 1.
- the process accelerated according to the invention is particularly suitable for producing phosphate coatings on steel, galvanized steel, aluminum or on surfaces which contain several of these metals. It is advantageously used to produce phosphate layers which are suitable both as a corrosion protection layer and layer for improving paint adhesion and as a sliding layer for cold forming.
- the phosphating solutions used to produce phosphate layers on metal surfaces can have further constituents. It is advantageous to use solutions for the phosphating of aluminum surfaces which additionally contain 0.1 to 5.0 g / l of fluoride, which can be present in the phosphating solution as free or complex-bound fluoride ion. Suitable complex fluorides are e.g. B. fluoroborates and / or fluorosilicates.
- Phosphating solutions which additionally contain Ni, Co and / or Fe ions can advantageously be used for the layer formation on galvanized steel. However, these ions should not be present in a total amount above 3.0 g / l. Salts of these metals are advantageously used in a concentration of 0.1 to 4.5 g / l as salts of the aforementioned simple or complex fluorides. Phosphating solutions containing nickel, cobalt and / or iron and fluoride are particularly well suited for the formation of layers on surfaces consisting of several metals. However, the total amount of nickel, cobalt and / or iron ions must not be greater than the amount of zinc ions.
- phosphating solutions which additionally contain a total of 0.3 to 5.0 g / l of a mixture of nonionic surfactants.
- sulfamic acid derivatives are impaired in phosphating solutions that contain calcium ions.
- Accelerators which do not form poorly soluble calcium salts for example benzoic acid sulfimide or benzene sulfanilides, are therefore used in such phosphating solutions according to the invention.
- the pH of the phosphating solution with which the metal surfaces intended for subsequent painting are brought into contact should be between 1.8 and 5.8, preferably between 2.0 and 3.5.
- the process accelerated according to the invention has the advantage of delivering well-formed phosphate coatings of up to 30 g / m 2 on metal surfaces with a total acidity of less than 40 points and with a free acidity of 20 points, which are then subjected to cold forming.
- the metal surfaces can be treated in any manner to form homogeneous phosphate layers. Diving and spraying systems and combined diving / spraying systems are particularly suitable.
- the treatment times for spraying are between 20 and 300, preferably between 30 and 180 seconds.
- well-formed phosphate layers of up to 22 g / m 2 were formed after only 300 seconds.
- the treatment times depend on the process conditions (temperature of the phosphating solution, pH value, spray pressure), the nature of the metal surfaces to be phosphated and the upstream treatment of the metals to be phosphated.
- the temperatures at which the metal surfaces can be brought into contact with phosphating solutions using the accelerators according to the invention in the phosphating agents are from 25 to 70 ° C., for the formation of phosphate layers with high coating weights, preferably between 45 to 60 ° C. and thus significantly below the commonly used Treatment temperatures. Treatment temperatures of 25 ° C are possible in special process combinations and specially adjusted phosphating solutions.
- the process accelerated according to the invention has the further advantage that the sludge formation is largely suppressed.
- the incrustation of the heating register is almost completely avoided.
- the sludge formation in the bath is considerably smaller than in the known phosphating baths which work with continuous or repeated additions of sodium nitrite as accelerators.
- the baths according to the invention need e.g. B. in diving operation and normal throughput only to be desludged every 12 to 15 months.
- the method accelerated according to the invention also has the advantage of still delivering excellent values with regard to paint adhesion and corrosion protection when the normal zinc phosphating technology is used.
- the process engineering advantages of normal zinc phosphating technology can be combined with the application engineering advantages of low zinc phosphating technology.
- the accelerated according to the invention provides the new and surprising effect that the zinc phosphate baths can be operated immediately with very high bath loads and low temperatures without incorporation. Furthermore, a particularly economical production of the desired phosphate coatings is possible. This is due to the low consumption of chemicals required to produce a certain layer weight.
- coating weights of 0.2 to 30 g / m 2 for steel and of 0.5 to 3.0 g / m 2 for galvanized steel can be achieved.
- the respective value results from the type of treatment, the treatment time, the accelerator concentration and the temperature of the phosphating bath solutions used.
- the process accelerated according to the invention is carried out within a process sequence known to the person skilled in the art, which consists of cleaning the metal surfaces, water rinsing, optionally preactivation with a solution containing titanium salt, phosphating with formation of the phosphate layer, water rinsing, post-treatment (passivation) and rinsing with demineralized water.
- a characteristic feature of the process accelerated according to the invention is furthermore that the preactivation with a solution containing titanium salt can be dispensed with.
- the process sequence consists of a cleaning step with a strongly alkaline cleaner, subsequent rinsing, phosphating with the formation of the phosphate layer, post-treatment (passivation) and rinsing with deionized water.
- the process for the preparation of phosphate coatings on steel and iron using an acidic zinc phosphate solution accelerated according to the invention at temperatures of 45 to 60 ° C in the immersion process is characterized in that bath solutions can be used which are prepared with aqueous acidic concentrates in which the weight ratio is widely variable from zinc to phosphate without the advantages according to the invention, such as reduced sludge accumulation, extremely fine crystalline layer formation, possibly also eliminating the need for preactivation with solutions containing titanium salts, fully formed phosphate layers, being lost at low treatment temperatures.
- a weight ratio of zinc to phosphate of 1: 1 to 12 has proven to be particularly advantageous.
- the fine-grained phosphate coatings offer excellent corrosion protection, as a review based on the test methods mentioned in the examples showed. It also shows that the fine-grained phosphate layers in particular represent an excellent anchorage for subsequent applied lacquer coatings.
- the process accelerated according to the invention is particularly advantageous as a pretreatment before electrocoating, in particular cathodic electrocoating.
- the metal surfaces covered with the phosphate layers can not only be painted, but can also be coated with different types of materials.
- Another important advantage is that the process according to the process accelerated according to the invention is characterized by reduced sludge and crust formation in the phosphating plants, which leads to economical process management and an extended service life of the phosphating solution.
- the phosphating solution used in carrying out the process accelerated according to the invention is normally prepared as an acid concentrate and diluted accordingly before use.
- the Concentrate can have a sufficiently high free acid content to avoid solid separation during storage, when the temperature drops or during transport.
- the concentrate is diluted to the desired concentration and adjusted to the required pH or the free acid content.
- the continuously used phosphating solution can be supplemented with the aid of a supplementary solution which contains all active constituents or with the use of several supplementary solutions which contain all active constituents in their entirety.
- Concentrate A was first prepared by mixing the following components in a container made of plastic or stainless steel:
- Cold-rolled steel sheets were subjected to the following process: First, the sheets were spray-treated with an alkaline cleaner (based on sodium hydroxide, pentasodium tripolyphosphate and surfactant) at 55 ° C. for 25 seconds. This was followed by a second cleaning by spraying with an alkaline cleaner (based on disodium hydrogenphosphate, activating titanium salt and surfactant) at 45 ° C. for 25 seconds. Then it was rinsed with cold water for 25 seconds.
- an alkaline cleaner based on sodium hydroxide, pentasodium tripolyphosphate and surfactant
- the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 60 seconds.
- the phosphated sheets were rinsed cold for 25 seconds and then with a solution containing Cr (VI) / Cr (III) ions at a pH from 4.0 treated at 30 ° C for 30 sec. in spraying. This was followed by rinsing with fully demineralized water for 10 seconds. Finally, the sheets were dried in an oven at 110 ° C. for 4 minutes.
- the sheets treated in this way were dip-coated cathodically with an electrodeposition paint from BASF.
- the tests to determine resistance to corrosion and various other physical properties gave excellent results.
- the sheets were immersed in an alkaline cleaner (based on sodium hydroxide, water glass, sodium orthophosphate and surfactant) at 70 ° C for 10 minutes. treated. Then 3 min. rinsed with water. It was then treated with a hydrochloric acid-containing pickling agent at 25 ° C. for 25 min. stained. This was followed by treatment with the phosphating solution described above by immersion at 50 ° C. for 10 minutes. The phosphated sheets were rinsed with water for 3 minutes and then with a solution containing Cr (VI) / Cr (III) ions at a pH of 4.0 at 40 ° C. for 3 min. treated in diving and finally with demineralized water for 2 min. rinsed.
- an alkaline cleaner based on sodium hydroxide, water glass, sodium orthophosphate and surfactant
- the sheets treated in this way were dip-coated cathodically with an electro-dip coating from Wiederhold / ICI.
- the phosphated and painted sheets were then subjected to tests to determine corrosion resistance and other physical properties. The properties observed in each case were excellent.
- the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 60 seconds.
- the phosphated sheets were rinsed cold for 25 seconds and then with a solution containing Cr (VI) / Cr (III) ions at a pH from 4.0 treated at 30 ° C for 30 sec. in spraying. This was followed by rinsing with demineralized water for 10 seconds. Finally, the sheets were dried in an oven at 110 ° C. for 4 minutes.
- the sheets treated in this way were dip-coated cathodically with an electrodeposition paint from BASF.
- the tests to determine resistance to corrosion and various other physical properties gave excellent results.
- Cold-rolled steel sheets were subjected to the following process steps: First, the sheets were treated with an alkaline cleaner (based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant) at 55 ° C. for 60 s by spraying. Then it was rinsed with cold water for 30 seconds.
- an alkaline cleaner based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant
- the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 90 s.
- the phosphated sheets were rinsed cold and then with a Cr (VI) / Cr (III) - Solution containing ions treated at pH 4.0 at room temperature for 30 s by spraying.
- the sheets treated in this way were dip-coated cathodically with an electrodeposition paint from BASF.
- the tests to determine resistance to corrosion and various other physical properties gave excellent results.
- Cold-rolled steel sheets were subjected to the following process steps: First, the sheets were treated with an alkaline cleaner (based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant) at 55 ° C. for 60 s by spraying. Then it was rinsed with cold water for 30 seconds.
- an alkaline cleaner based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant
- the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 90 s.
- the phosphated sheets were rinsed cold for 30 s and then sprayed with a solution containing Cr (VI) / Cr (III) ions at a pH of 4.0 at room temperature for 30 s.
- a concentrate was prepared by mixing the following ingredients in a stainless steel container.
- the phosphated blanks were rinsed with water for 3 minutes and then soaped with a soap-containing aqueous solution (6% sodium stearate, 1% sodium myristate) at 80 ° C. for 5 minutes.
- a soap-containing aqueous solution 6% sodium stearate, 1% sodium myristate
- the phosphated blanks were rinsed with water for 3 minutes and then soaped with a soap-containing aqueous solution (6% sodium stearate, 1% sodium myristate) at 80 ° C. for 5 minutes.
- a soap-containing aqueous solution 6% sodium stearate, 1% sodium myristate
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Materials For Medical Uses (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Claims (7)
en tant que composant accélérateur et affinant le grain des couches, en une quantité de 0,1 à 6 g/I, dans des solutions de phosphatation à base de phosphate de zinc et/ou phosphate de fer et/ou phosphate de fer et zinc, qui servent à l'application de revêtements de phosphate sur des surfaces métalliques, en plus d'autres composants utilisés habituellement dans de telles solutions de phosphatation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT84105731T ATE39003T1 (de) | 1983-07-19 | 1984-05-19 | Verfahren und mittel zum beschleunigten und schichtverfeinernden aufbringen von phosphatueberzuegen auf metalloberflaechen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE3325974 | 1983-07-19 | ||
DE19833325974 DE3325974A1 (de) | 1983-07-19 | 1983-07-19 | Verfahren und universell anwendbare mittel zum beschleunigten aufbringen von phosphatueberzuegen auf metalloberflaechen |
Publications (2)
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EP0134895A1 EP0134895A1 (fr) | 1985-03-27 |
EP0134895B1 true EP0134895B1 (fr) | 1988-11-30 |
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EP84105731A Expired EP0134895B1 (fr) | 1983-07-19 | 1984-05-19 | Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques |
Country Status (11)
Country | Link |
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US (1) | US4680064A (fr) |
EP (1) | EP0134895B1 (fr) |
JP (1) | JPS6039168A (fr) |
AT (1) | ATE39003T1 (fr) |
AU (1) | AU567748B2 (fr) |
BR (1) | BR8403587A (fr) |
CA (1) | CA1236952A (fr) |
DE (2) | DE3325974A1 (fr) |
ES (1) | ES534422A0 (fr) |
FI (1) | FI77268C (fr) |
ZA (1) | ZA845551B (fr) |
Cited By (1)
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DE102006024614A1 (de) * | 2006-05-26 | 2007-11-29 | Schaeffler Kg | Verfahren zum Behandeln einer Wälzlagerkomponente und Wälzlagerkomponente |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE3631667A1 (de) * | 1986-09-18 | 1988-03-24 | Collardin Gmbh Gerhard | Schichtbildende passivierung bei multimetall-verfahren |
DE4241134A1 (de) * | 1992-12-07 | 1994-06-09 | Henkel Kgaa | Verfahren zur Phosphatierung von Metalloberflächen |
US5427632A (en) * | 1993-07-30 | 1995-06-27 | Henkel Corporation | Composition and process for treating metals |
US5449415A (en) * | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
DE4417965A1 (de) * | 1994-05-21 | 1995-11-23 | Henkel Kgaa | Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren |
EP1453989A4 (fr) * | 2001-12-13 | 2005-03-23 | Henkel Kgaa | Utilisation d'hydroxylamines substituees pour les procedes de phosphatation de metal |
WO2005071139A1 (fr) * | 2004-01-13 | 2005-08-04 | Mccully Timothy R | Composition et procede de formation de surfaces contenant du phosphate sur des composes dans des zones de combustion d'hydrocarbures |
AU2006348586A1 (en) * | 2006-09-18 | 2008-03-27 | Henkel Ag & Co. Kgaa | Non-chrome thin organic-inorganic hybrid coating on zinciferous metals |
BR112015021680A2 (pt) * | 2013-03-14 | 2017-07-18 | Buckman Laboratories Int Inc | método para inibir corrosão de uma superfície metálica |
WO2018221797A1 (fr) * | 2016-06-01 | 2018-12-06 | 주식회사 천우테크 | Agent de traitement de décapage et de couche de passivation destiné à éliminer les dépôts et la rouille de zones de soudage d'un tuyau et d'une structure en acier inoxydable |
EP3676419B1 (fr) * | 2017-08-31 | 2023-10-11 | Chemetall GmbH | Procédé amélioré de phosphatage sans nickel des surfaces métalliques |
CN111850534B (zh) * | 2020-06-16 | 2022-03-01 | 中国石油天然气集团有限公司 | 一种马氏体不锈钢油管低应力预钝化膜及其制备方法 |
Citations (1)
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US3923554A (en) * | 1974-02-07 | 1975-12-02 | Detrex Chem Ind | Phosphate coating composition and method |
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GB599778A (en) * | 1945-11-07 | 1948-03-19 | Pyrene Co Ltd | Improvements relating to the production of phosphate coatings on metal |
NL102953C (fr) * | 1900-01-01 | |||
FR1045538A (fr) * | 1951-11-28 | 1953-11-26 | Cie D Applic Chimiques A L Ind | Perfectionnement à la phosphatation superficielle des métaux ferreux, du zinc et de leurs alliages |
DE1219766B (de) * | 1961-07-28 | 1966-06-23 | N Izsledovatelski I Mash I Met | Verfahren zur kalten Phosphatierung von kohlenstoffarmem Stahl |
AT282285B (de) * | 1965-12-22 | 1970-06-25 | Plaut Fa J | Zinkphosphatüberzüge |
FR2110784A5 (fr) * | 1970-10-30 | 1972-06-02 | Parker Ste Continentale | |
JPS506418B1 (fr) * | 1971-07-06 | 1975-03-13 | ||
DE2241798C2 (de) * | 1972-08-25 | 1982-03-11 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Phosphatierung von Eisen und Stahl |
SU550460A1 (ru) * | 1973-12-06 | 1977-03-15 | Предприятие П/Я Г-4347 | Вдный раствор дл одновременного обезжиривани , травлени и фосфатировани металлической поверхности |
GB1542222A (en) * | 1977-01-06 | 1979-03-14 | Pyrene Chemical Services Ltd | Phosphate coating compositions |
US4149909A (en) * | 1977-12-30 | 1979-04-17 | Amchem Products, Inc. | Iron phosphate accelerator |
JPS5811513B2 (ja) * | 1979-02-13 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
DE3016576A1 (de) * | 1980-04-30 | 1981-11-05 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung |
DE3118375A1 (de) * | 1981-05-09 | 1982-11-25 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung |
US4498935A (en) * | 1981-07-13 | 1985-02-12 | Parker Chemical Company | Zinc phosphate conversion coating composition |
-
1983
- 1983-07-19 DE DE19833325974 patent/DE3325974A1/de not_active Withdrawn
-
1984
- 1984-05-19 AT AT84105731T patent/ATE39003T1/de not_active IP Right Cessation
- 1984-05-19 DE DE8484105731T patent/DE3475412D1/de not_active Expired
- 1984-05-19 EP EP84105731A patent/EP0134895B1/fr not_active Expired
- 1984-07-18 AU AU30783/84A patent/AU567748B2/en not_active Ceased
- 1984-07-18 BR BR8403587A patent/BR8403587A/pt not_active IP Right Cessation
- 1984-07-18 ZA ZA845551A patent/ZA845551B/xx unknown
- 1984-07-18 CA CA000459189A patent/CA1236952A/fr not_active Expired
- 1984-07-18 FI FI842886A patent/FI77268C/fi not_active IP Right Cessation
- 1984-07-18 ES ES534422A patent/ES534422A0/es active Granted
- 1984-07-19 JP JP59151112A patent/JPS6039168A/ja active Pending
-
1985
- 1985-09-27 US US06/781,316 patent/US4680064A/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3923554A (en) * | 1974-02-07 | 1975-12-02 | Detrex Chem Ind | Phosphate coating composition and method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006024614A1 (de) * | 2006-05-26 | 2007-11-29 | Schaeffler Kg | Verfahren zum Behandeln einer Wälzlagerkomponente und Wälzlagerkomponente |
Also Published As
Publication number | Publication date |
---|---|
FI77268C (fi) | 1989-02-10 |
BR8403587A (pt) | 1985-06-25 |
US4680064A (en) | 1987-07-14 |
DE3475412D1 (en) | 1989-01-05 |
AU567748B2 (en) | 1987-12-03 |
ATE39003T1 (de) | 1988-12-15 |
FI842886A (fi) | 1985-01-20 |
ES8600972A1 (es) | 1985-10-16 |
AU3078384A (en) | 1985-01-24 |
JPS6039168A (ja) | 1985-02-28 |
ES534422A0 (es) | 1985-10-16 |
FI842886A0 (fi) | 1984-07-18 |
ZA845551B (en) | 1985-03-27 |
CA1236952A (fr) | 1988-05-24 |
EP0134895A1 (fr) | 1985-03-27 |
DE3325974A1 (de) | 1985-01-31 |
FI77268B (fi) | 1988-10-31 |
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