EP0433118B1 - Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath - Google Patents
Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath Download PDFInfo
- Publication number
- EP0433118B1 EP0433118B1 EP90403233A EP90403233A EP0433118B1 EP 0433118 B1 EP0433118 B1 EP 0433118B1 EP 90403233 A EP90403233 A EP 90403233A EP 90403233 A EP90403233 A EP 90403233A EP 0433118 B1 EP0433118 B1 EP 0433118B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- ions
- acid
- ion
- zinc
- 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 - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 title description 10
- 229910052751 metal Inorganic materials 0.000 title description 5
- 239000002184 metal Substances 0.000 title description 5
- 239000012141 concentrate Substances 0.000 title description 3
- -1 nitrate ions Chemical class 0.000 claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000002738 chelating agent Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims 1
- 235000003704 aspartic acid Nutrition 0.000 claims 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims 1
- 235000013922 glutamic acid Nutrition 0.000 claims 1
- 239000004220 glutamic acid Substances 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 235000011090 malic acid Nutrition 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 10
- 239000010452 phosphate Substances 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 229910000760 Hardened steel Inorganic materials 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- 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 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001272377 Uredo rangelii Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- 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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates containing also phosphates
Definitions
- the subject of the invention is a process for the chemical conversion of metallic substrates, in particular based on iron or zinc-plated steel, with a view to increasing their resistance to corrosion, their ability to deformation or simultaneously both.
- These treatments can be carried out on the substrates to be treated by spraying or by immersion.
- the substrates thus treated can be used as they are or else receive a subsequent application of lubricant, protective oil or paint.
- a phosphating bath it is possible for a phosphating bath to contain from 2 to 50 g / l of aliphatic polyhydroxymonocarboxylic acid, such as gluconic acid.
- the layer weight can be increased by adding an organic polyacid in an accelerated chlorate phosphating bath and practically free of ferrous ions.
- the object of the invention is, above all, to remedy this drawback and to provide a chemical conversion bath which, while providing performance equivalent to that of the process described in patent FR-A-2,531,457, can be regenerated by continued.
- the chemical conversion process is characterized in that it comprises the implementation, at the time of the phosphating step proper, of a zinc conversion bath free of chlorate ions and of a temperature from 70 to 99 ° C, containing from 0.5 to 25 g / l of zinc ion, from 5 to 40 g / l of phosphate ions, from 2 to 40 g / l of nitrate ions as well as from 0 , 1 to 15 g / l of iron ions and 21 to 100 g / l of at least one organic chelating agent consisting of a polycarboxylic acid chosen from the group comprising oxalic, malic, glutamic, tartaric, aspartic, malonic acids and citric acid, or a salt thereof.
- the salts of the above polycarboxylic acids are chosen from those of alkali metals, alkaline earth metals, ammonium, iron, zinc, manganese, molybdenum, cobalt and nickel.
- the zinc ion present in an amount of 0.5 to 25 g / l, can be introduced in any suitable way, and in particular in the form of its salts with nitric, phosphoric, carbonic, gluconic, citric acids. , or in the form of its oxide. It can be combined with all the metals commonly used in a phosphating bath such as, for example, manganese, nickel, cobalt, calcium, magnesium.
- the iron ions present in a proportion of 0.1 to 15 g / l, can be introduced either by dissolving iron in the solid state, such as for example iron wool, massive pieces or scrap steel parts, either thanks to iron salts with sulfuric, hydrochloric, hydrofluoric, phosphoric or nitric acids; it can be the ferrous ion, the ferric ion or a mixture of the two.
- the phosphate ions on the one hand and the nitrate ions on the other hand are each present in the bath in a proportion of up to 40 g / l.
- the bath used in accordance with the invention may also contain hydrofluoric, fluosilicic or fluoboric acids or more of them to regulate the balance between the pickling of the support by the acid solution and the growth of the crystalline layer.
- the coatings produced by implementing the process according to the invention provide, in the sense of the test according to ASTM B-117, a resistance to salt spray comparable to that obtained according to patent FR-A-2,531,457 while allowing continuous regeneration.
- the substrates treated by implementing the process according to the invention can be stored or used without further protection, but it is also possible to paint these substrates in order to further increase their resistance to corrosion; they can possibly be deformed cold after a possible operation of applying a lubricant.
- it contains from 0.02 to 3 g / l of nickel, cobalt or copper.
- the chemical conversion bath used in accordance with the invention is applied by spraying onto the metal substrate to be treated or by immersion of the substrate in the bath, immersion being preferred.
- the process is simplified by eliminating the chromic passivation and protection steps, subsequent to the chemical phosphating conversion. and necessary in the processes of the prior art.
- a conversion bath is constituted according to the prior art containing, in addition to water, the following ions: Zn++: 6 g / l Total PO4: 16.7 g / l NO 3 - : 10 g / l Total Fe: 1 g / l Ni++: 0.2 g / l
- the plates thus prepared are subjected to 5% salt spray test (according to ASTM B-117).
- a conversion bath is prepared for implementation in the process according to the invention by adding to the bath according to Example 1 an amount of 30 g / l of citric acid.
- the free acidity of the new bath is brought to 18/19 points.
- the cold-rolled steel plates are treated in the same way as in Example 1 and a 10% rusting is obtained locally after 150 hours of exposure.
- Citric acid content of the bath (g / l) Salt spray test Beginning of rust Rust at 50% 1 0 immediate less than 1 hour 2 10 5 a.m. 8 a.m. 3 30 sailing after 100 h some rust spots after 150 h
- the purpose of this example is to show the possibility of applying the process to various industrial parts. Parts of HRC 55 case hardened steel (0.55% carbon at heart) and mild steel XC 10 (0.1% carbon) are treated.
- composition A Composition A
- the treatment sequence is the same as that described in Example 1, with the exception of step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out in an aqueous solution containing 7.75% v / v d '75% phosphoric acid, for 2 minutes at a temperature of 60 ° C.
- the bath is heated to 95 ° C. and the free acidity is brought to a value of 20 points with sodium hydroxide.
- Cold rolled steel sheets of the ZES type are treated in a sequence identical to that described in Example 1 (the conversion step using the above-mentioned bath), with the exception of steps 3 and 4 which are omitted . After treatment, the sheets are tested in a salt spray test (according to ASTM B-117) and, after an exposure of 400 h, no development of rust is observed.
Landscapes
- 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)
- Manufacture And Refinement Of Metals (AREA)
- Chemically Coating (AREA)
- Catalysts (AREA)
Abstract
Description
L'invention a pour objet un procédé de conversion chimique de substrats métalliques, notamment à base de fer ou d'acier zingué, en vue d'accroître leur résistance à la corrosion, leur aptitude à la déformation ou simultanément les deux.The subject of the invention is a process for the chemical conversion of metallic substrates, in particular based on iron or zinc-plated steel, with a view to increasing their resistance to corrosion, their ability to deformation or simultaneously both.
Elle vise aussi un bain de conversion chimique propre à être mis en oeuvre dans ce procédé, ainsi qu'un concentré pour la préparation du bain.It also relates to a chemical conversion bath suitable for being used in this process, as well as a concentrate for the preparation of the bath.
Il est connu de réaliser la conversion chimique de substrats métalliques par des traitements classiques de phosphatation cristalline qui conduisent au dépôt, à la surface du métal, d'une couche de phosphates insolubles.It is known to carry out the chemical conversion of metallic substrates by conventional crystalline phosphating treatments which lead to the deposition, on the surface of the metal, of a layer of insoluble phosphates.
Les traitements de phosphatation cristalline connus mettent généralement en oeuvre des bains acides qui contiennent au moins les constituants suivants:
- l'acide orthophosphorique H₃PO₄
- un ion phosphate primaire H₂PO4 -
- un ou plusieurs métaux choisis parmi le zinc ou le fer, le manganèse, le nickel, le cuivre, le cobalt, le calcium,
- au moins un accélérateur constitué par un agent oxydant tel que les ions chlorate, nitrate, le nitrite ou le métanitrobenzène sulfonate de sodium.
- orthophosphoric acid H₃PO₄
- a primary phosphate ion H₂PO 4 -
- one or more metals chosen from zinc or iron, manganese, nickel, copper, cobalt, calcium,
- at least one accelerator consisting of an oxidizing agent such as sodium chlorate, nitrate, nitrite or metanitrobenzene sulfonate.
Ces traitements peuvent être effectués sur les substrats à traiter par pulvérisation ou par immersion.These treatments can be carried out on the substrates to be treated by spraying or by immersion.
Ils s'insèrent dans une séquence d'étapes opérationnelles pouvant comprendre:
- une ou plusieurs étapes de dégraissage,
- une ou plusieurs étapes de rinçage,
- éventuellement, une ou plusieurs étapes de décapage, puis de rinçage,
- éventuellement, une étape de conditionnement de surface,
- l'étape de phosphatation proprement dite,
- une ou plusieurs étapes de rinçage,
- éventuellement une étape de passivation, généralement en milieu chromique et une étape de rinçage,
- éventuellement, une étape de séchage ou d'étuvage.
- one or more degreasing steps,
- one or more rinsing steps,
- possibly one or more stages of pickling, then rinsing,
- optionally, a surface conditioning step,
- the actual phosphating step,
- one or more rinsing steps,
- possibly a passivation step, generally in a chromic medium and a rinsing step,
- optionally, a drying or baking step.
Les substrats ainsi traités peuvent être utilisés tels quels ou bien recevoir une application ultérieure de lubrifiant, d'huile de protection ou de peinture.The substrates thus treated can be used as they are or else receive a subsequent application of lubricant, protective oil or paint.
La nature et la composition de la couche de phosphates insolubles obtenue dépendent essentiellement:
- de la nature du substrat,
- de la composition du bain de phosphatation,
- du mode d'application du produit (aspersion ou immersion),
- des étapes de prétraitement.
- the nature of the substrate,
- the composition of the phosphating bath,
- the method of application of the product (sprinkling or immersion),
- pretreatment steps.
L'art antérieur décrit divers perfectionnements aux bains de conversion chimique visant à améliorer les performances de ceux-ci.The prior art describes various improvements to chemical conversion baths aimed at improving their performance.
Ainsi, selon le brevet FR-A-1 362 202, on obtient une amélioration de la tenue à la corrosion des couches de phosphatation par ajout d'une faible quantité (jusqu' à 2%) et préférentiellement comprise entre 0,5 et 1,5%) d'agents complexants organiques; des performances de tenue au brouillard salin ASTM B-117 inférieures ou égales à 25 heures sont rapportées dans ce brevet.Thus, according to patent FR-A-1 362 202, an improvement in the corrosion resistance of the phosphating layers is obtained by adding a small amount (up to 2%) and preferably between 0.5 and 1 , 5%) organic complexing agents; ASTM B-117 salt spray performance less than or equal to 25 hours is reported in this patent.
Selon le brevet US-A-3 116 178, il est possible de faire comporter à un bain de phosphatation de 2 à 50 g/l d'acide polyhydroxymonocarboxylique aliphatique, tel que l'acide gluconique.According to US Pat. No. 3,116,178, it is possible for a phosphating bath to contain from 2 to 50 g / l of aliphatic polyhydroxymonocarboxylic acid, such as gluconic acid.
Selon le brevet FR-A-1 585 660, le poids de couche peut être accru par addition d'un polyacide organique dans un bain de phosphatation accéléré au chlorate et à peu près exempt d'ions ferreux.According to patent FR-A-1,585,660, the layer weight can be increased by adding an organic polyacid in an accelerated chlorate phosphating bath and practically free of ferrous ions.
Enfin, selon le brevet FR-A-2 531 457, l'association d'un agent chélatant et d'un polyphosphate soluble permet d'obtenir des couches dont la tenue à la corrosion est sensiblement améliorée, des tenues au brouillard salin pouvant atteindre 310 heures étant mentionnées en rapport avec des pièces uniquement phosphatées.Finally, according to patent FR-A-2 531 457, the combination of a chelating agent and a soluble polyphosphate makes it possible to obtain layers whose resistance to corrosion is appreciably improved, resistance to salt spray being able to reach 310 hours being mentioned in connection with phosphate-only parts.
Le brevet français en question rappelle qu'un excès de polyphosphates peut empêcher la formation de la couche cristalline et propose de faire mûrir les bains revendiqués par évolution du pH avant mise en oeuvre.The French patent in question recalls that an excess of polyphosphates can prevent the formation of the crystalline layer and proposes to cure the baths claimed by evolution of the pH before implementation.
Le mûrissement en question n'étant pas instantané, les opérations de régénération du bain sont obligatoirement discontinues, ce qui constitue un inconvénient, la plupart des bains industriels étant régénérés en continu.Since the ripening in question is not instantaneous, the bath regeneration operations are necessarily discontinuous, which constitutes a drawback, most industrial baths being regenerated continuously.
L'invention a pour but, surtout, de remédier à cet inconvénient et de fournir un bain de conversion chimique qui, tout en procurant des performances équivalentes à celles du procédé décrit dans le brevet FR-A-2 531 457, peut être régénéré en continu.The object of the invention is, above all, to remedy this drawback and to provide a chemical conversion bath which, while providing performance equivalent to that of the process described in patent FR-A-2,531,457, can be regenerated by continued.
En conséquence, le procédé de conversion chimique est caractérisé par le fait qu'il comporte la mise en oeuvre, au moment de l'étape de phosphatation proprement dite, d'un bain de conversion au zinc exempt d'ions chlorate et d'une température de 70 à 99°C, contenant de 0,5 à 25 g/l d'ion zinc, de 5 à 40 g/l d'ions phosphates, de 2 à 40 g/l d'ions nitrate ainsi que de 0,1 à 15 g/l d'ions fer et de 21 à 100 g/l d'au moins un agent chélatant organique constitué par un acide polycarboxylique choisi dans le groupe comprenant les acides oxalique, malique, glutamique, tartrique, aspartique, malonique et l'acide citrique, ou un de ses sels.Consequently, the chemical conversion process is characterized in that it comprises the implementation, at the time of the phosphating step proper, of a zinc conversion bath free of chlorate ions and of a temperature from 70 to 99 ° C, containing from 0.5 to 25 g / l of zinc ion, from 5 to 40 g / l of phosphate ions, from 2 to 40 g / l of nitrate ions as well as from 0 , 1 to 15 g / l of iron ions and 21 to 100 g / l of at least one organic chelating agent consisting of a polycarboxylic acid chosen from the group comprising oxalic, malic, glutamic, tartaric, aspartic, malonic acids and citric acid, or a salt thereof.
Les sels des susdits acides polycarboxyliques sont choisis parmi ceux des métaux alcalins, alcalino-terreux, d'ammonium, de fer, de zinc, de manganèse, de molybdène, de cobalt et de nickel.The salts of the above polycarboxylic acids are chosen from those of alkali metals, alkaline earth metals, ammonium, iron, zinc, manganese, molybdenum, cobalt and nickel.
L'ion zinc, présent à raison d'une proportion de 0,5 à 25 g/l, peut être introduit de toute manière appropriée, et notamment sous la forme de ses sels avec les acides nitrique, phosphorique, carbonique, gluconique, citrique, ou sous la forme de son oxyde. Il peut être associé à tous les métaux couramment utilisés dans un bain de phosphatation comme, par exemple, le manganèse, le nickel, le cobalt, le calcium, le magnésium.The zinc ion, present in an amount of 0.5 to 25 g / l, can be introduced in any suitable way, and in particular in the form of its salts with nitric, phosphoric, carbonic, gluconic, citric acids. , or in the form of its oxide. It can be combined with all the metals commonly used in a phosphating bath such as, for example, manganese, nickel, cobalt, calcium, magnesium.
Les ions fer, présents à raison d'une proportion de 0,1 à 15 g/l, peuvent être introduits soit par dissolution de fer à l'état solide, comme par exemple de la paille de fer, des pièces massives ou des rebuts de pièces en acier, soit grâce à des sels de fer avec les acides sulfurique, chlorhydrique, fluorhydrique, phosphorique ou nitrique; il peut s'agir de l'ion ferreux, de l'ion ferrique ou d'un mélange des deux.The iron ions, present in a proportion of 0.1 to 15 g / l, can be introduced either by dissolving iron in the solid state, such as for example iron wool, massive pieces or scrap steel parts, either thanks to iron salts with sulfuric, hydrochloric, hydrofluoric, phosphoric or nitric acids; it can be the ferrous ion, the ferric ion or a mixture of the two.
Les ions phosphates d'une part et nitrate d'autre part sont présents chacun dans le bain en une proportion pouvant atteindre 40 g/l.The phosphate ions on the one hand and the nitrate ions on the other hand are each present in the bath in a proportion of up to 40 g / l.
Le bain utilisé conformément à l'invention peut également contenir les acides fluorhydrique, fluosilicique ou fluoborique ou plusieurs d'entre eux pour régler l'équilibre entre le décapage du support par la solution acide et la croissance de la couche cristalline.The bath used in accordance with the invention may also contain hydrofluoric, fluosilicic or fluoboric acids or more of them to regulate the balance between the pickling of the support by the acid solution and the growth of the crystalline layer.
Le bain utilisé conformément à l'invention est préparé par dilution à partir d'un concentré caractérisé par le fait qu'il contient
- jusqu'à 500 g/l d'acide polycarbonylique, notamment d'ion citrate
- jusqu'à 200 g/l d'ions phosphate
- jusqu'à 125 g/l d'ions zinc
- jusqu'à 200 g/l d'ion nitrate.
- up to 500 g / l polycarbonylic acid, especially citrate ion
- up to 200 g / l of phosphate ions
- up to 125 g / l zinc ions
- up to 200 g / l of nitrate ion.
Les revêtements produits par mise en oeuvre du procédé conforme à l'invention procurent, au sens du test selon la norme ASTM B-117, une résistance au brouillard salin comparable à celle obtenue selon le brevet FR-A-2.531.457 tout en autorisant une régénération continue.The coatings produced by implementing the process according to the invention provide, in the sense of the test according to ASTM B-117, a resistance to salt spray comparable to that obtained according to patent FR-A-2,531,457 while allowing continuous regeneration.
Les substrats traités par mise en oeuvre du procédé conforme à l'invention peuvent être stockés ou utilisés sans protection ultérieure mais il est possible également de peindre ces substrats afin d'augmenter encore leur tenue à la corrosion; ils peuvent éventuellement être déformés à froid après une opération éventuelle d'application d'un lubrifiant.The substrates treated by implementing the process according to the invention can be stored or used without further protection, but it is also possible to paint these substrates in order to further increase their resistance to corrosion; they can possibly be deformed cold after a possible operation of applying a lubricant.
Suivant un mode de réalisation avantageux du procédé conforme à l'invention, le bain mis en oeuvre contient :
- de 5 à 20 g/l d'ions phosphates
- de 21 à 60 g/l d'ion citrique
- de 2 à 40 g/l d'ion nitrate
- de 2 à 10 g/l d'ion zinc
- de 0,1 à 15 g/l de fer.
- from 5 to 20 g / l of phosphate ions
- from 21 to 60 g / l of citric ion
- from 2 to 40 g / l of nitrate ion
- from 2 to 10 g / l of zinc ion
- 0.1 to 15 g / l of iron.
Suivant une variante, il contient de 0,02 à 3 g/l de nickel, de cobalt ou de cuivre.According to a variant, it contains from 0.02 to 3 g / l of nickel, cobalt or copper.
Le bain de conversion chimique mis en oeuvre conformément à l'invention est appliqué par pulvérisation sur le substrat métallique à traiter ou par immersion du substrat dans le bain, l'immersion étant préférée.The chemical conversion bath used in accordance with the invention is applied by spraying onto the metal substrate to be treated or by immersion of the substrate in the bath, immersion being preferred.
Le procédé de conversion chimique conforme à l'invention comprend un ensemble d'étapes de traitement, à savoir:
- une ou plusieurs étapes de dégraissage,
- une ou plusieurs étapes de rinçage,
- éventuellement, une ou plusieurs étapes d'activation ou de décapage,
- une étape de rinçage,
- l'étape de conversion chimique proprement dite par mise en oeuvre du bain conforme à l'invention,
- une étape de rinçage,
- une étape de séchage.
- one or more degreasing steps,
- one or more rinsing steps,
- possibly one or more stages of activation or pickling,
- a rinsing step,
- the chemical conversion stage proper by implementing the bath according to the invention,
- a rinsing step,
- a drying step.
De par la tenue exceptionnelle à la corrosion sèche des couches de phosphatation obtenues avec le bain mis en oeuvre conformément à l'invention, le procédé se trouve simplifié par la suppression des étapes de passivation chromique et de protection, postérieures à la conversion chimique de phosphatation et nécessaires dans les procédés de l'art antérieur.Due to the exceptional resistance to dry corrosion of the phosphating layers obtained with the bath used in accordance with the invention, the process is simplified by eliminating the chromic passivation and protection steps, subsequent to the chemical phosphating conversion. and necessary in the processes of the prior art.
L'invention sera bien comprise grâce aux exemples non limitatifs qui suivent et dans lesquels sont indiqués des modes de réalisation avantageux du bain mis en oeuvre conformément à l'invention.The invention will be better understood thanks to the nonlimiting examples which follow and in which are indicated advantageous embodiments of the bath used in accordance with the invention.
On constitue un bain de conversion selon l'art antérieur contenant, outre l'eau, les ions suivants:
On porte sa température à 95°C; l'acidité libre est amenée dans la zone de fonctionnement à 8,0 points avec de la soude concentrée (l'acidité libre est déterminée en titrant 10 ml de solution froide avec une solution de soude N/10 jusqu'à pH = 3,6).Its temperature is brought to 95 ° C; the free acidity is brought into the operating zone at 8.0 points with concentrated soda (the free acidity is determined by titrating 10 ml of cold solution with an N / 10 soda solution until pH = 3, 6).
Des plaquettes d'acier laminé à froid à 0,02% de carbone de qualité ZES couramment utilisée dans l'industrie automobile, de dimensions 150 mm x 140 mm, sont soumises à la gamme de traitement suivante:
- Etape 1:
- Dégraissage alcalin en solution aqueuse à base des dégraissants commercialisés par la Société Demanderesse sous les marques RIDOLINE 1550 CF/2 (à 1,5% v/v) et RIDOSOL 550 CF (1,5% v/v).
Température: 60°C.
Temps de traitement: 3 minutes. - Etape 2:
- Rinçage froid à l'eau courante pendant 2 minutes.
- Etape 3:
- Décapage nitrique
Décapant: acide nitrique à 60% en solution aqueuse (10% v/v).
Température: 20°C.
Temps de traitement: 10 secondes. - Etape 4:
- Rinçage froid à l'eau courante pendant 1 minute.
- Etape 5:
- Conversion proprement dite à 95°C pendant 30 minutes.
- Etape 6:
- Rinçage à l'eau froide courante pendant 10 secondes.
- Etape 7:
- Séchage à l'étuve à une température d'environ 95°C pendant 10 minutes.
- Step 1 :
- Alkaline degreasing in aqueous solution based on degreasers sold by the Applicant Company under the brands RIDOLINE 1550 CF / 2 (at 1.5% v / v) and RIDOSOL 550 CF (1.5% v / v).
Temperature: 60 ° C.
Processing time: 3 minutes. - Step 2 :
- Cold rinse with running water for 2 minutes.
- Step 3 :
- Nitric pickling
Stripper: 60% nitric acid in aqueous solution (10% v / v).
Temperature: 20 ° C.
Processing time: 10 seconds. - Step 4 :
- Cold rinse with running water for 1 minute.
- Step 5:
- Conversion proper at 95 ° C for 30 minutes.
- Step 6 :
- Rinse with running cold water for 10 seconds.
- Step 7 :
- Dry in an oven at a temperature of around 95 ° C for 10 minutes.
Les plaquettes ainsi préparées sont soumises à l'épreuve du brouillard salin à 5% (selon la norme ASTM B-117).The plates thus prepared are subjected to 5% salt spray test (according to ASTM B-117).
Après 1 heure d'exposition, on a un enrouillement de 50% très homogène.After 1 hour of exposure, there is a very homogeneous 50% rustling.
On prépare un bain de conversion selon l'art antérieur en ajoutant au bain selon l'exemple 1 une quantité de 10 g/l d'acide citrique. L'acidité libre du bain est amenée à 15,0 points. On réalise le même traitement que précédemment sur les mêmes plaques d'acier laminé à froid. On obtient, au bout de 8 heures d'exposition, un enrouillement homogène de 50%.Preparing a conversion bath according to the prior art by adding to the bath according to Example 1 an amount of 10 g / l of citric acid. The free acidity of the bath is brought to 15.0 points. The same treatment is carried out as above on the same cold-rolled steel plates. Obtained, after 8 hours of exposure, a homogeneous scalding of 50%.
On prépare un bain de conversion pour mise en oeuvre dans le procédé conforme à l'invention en ajoutant au bain selon l'exemple 1 une quantité de 30 g/l d'acide citrique. L'acidité libre du nouveau bain est amenée à 18/19 points. On traite de la même manière que dans l'exemple 1 des plaques d'acier laminé à froid analogues et l'on obtient localement, au bout de 150 heures d'exposition, un enrouillement de 10%.
Cet exemple a pour but de montrer la possibilité d'appliquer le procédé à des pièces industrielles variées. On réalise le traitement de pièces en acier cémenté HRC 55 (à 0,55% de carbone à coeur) et en acier doux XC 10 (à 0,1% de carbone).The purpose of this example is to show the possibility of applying the process to various industrial parts. Parts of HRC 55 case hardened steel (0.55% carbon at heart) and mild steel XC 10 (0.1% carbon) are treated.
On prépare les trois compositions suivantes:The following three compositions are prepared:
On mélange 56,7 g d'eau, 20 g d'acide citrique et 22,3 g d'acide phosphorique à 75%. On dissout dans ce mélange 1 g de fer métallique.56.7 g of water, 20 g of citric acid and 22.3 g of 75% phosphoric acid are mixed. 1 g of metallic iron is dissolved in this mixture.
On mélange 46,7 g d'eau, 30 g d'acide citrique et 22,3 g d'acide phosphorique à 75%. On dissout dans ce mélange 1 g de fer métallique.46.7 g of water, 30 g of citric acid and 22.3 g of 75% phosphoric acid are mixed. 1 g of metallic iron is dissolved in this mixture.
On dissout dans un mélange contenant 74,8 g d'eau et 16,7 g d'acide nitrique à 60%, 7,5 g d'oxyde de zinc et 1 g de nitrate de nickel à 20% de nickel.Dissolve in a mixture containing 74.8 g of water and 16.7 g of 60% nitric acid, 7.5 g of zinc oxide and 1 g of nickel nitrate of 20% nickel.
La séquence de traitement est la même que celle décrite dans l'exemple 1, à l'exception de l'étape 3, le décapage nitrique étant remplacé par un décapage phosphorique aqueux réalisé dans une solution aqueuse contenant 7,75% v/v d'acide phosphorique à 75%, pendant 2 minutes à une température de 60°C.The treatment sequence is the same as that described in Example 1, with the exception of step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out in an aqueous solution containing 7.75% v / v d '75% phosphoric acid, for 2 minutes at a temperature of 60 ° C.
Les bains mis en oeuvre au moment de l'étape de conversion proprement dite sont constitués comme suit:
- . Bain 1 :
- - 800 ml d'eau
- 100 ml de composition A
- 100 ml de composition C - . Bain 2 :
- - 800 ml d'eau
- 100 ml de composition B
- 100 ml de composition C.
- . Bath 1:
- - 800 ml of water
- 100 ml of composition A
- 100 ml of composition C - . Bath 2:
- - 800 ml of water
- 100 ml of composition B
- 100 ml of composition C.
Deux séries de pièces en acier, respectivement de qualité XC 10 et HRC 55, ayant été soumises à la séquence de traitement selon l'exemple 1 avec mise en oeuvre du bain 1 pour les pièces en acier XC 10 et du bain 2 pour les pièces en acier HRC 55, sont soumises au test du brouillard salin selon norme ASTM B-117 et on note le temps au bout duquel apparaît la rouille rouge.Two series of steel parts, of quality XC 10 and HRC 55 respectively, having been subjected to the treatment sequence according to Example 1 with the use of bath 1 for steel parts XC 10 and bath 2 for parts made of HRC 55 steel, are subjected to the salt spray test according to standard ASTM B-117 and the time after which the red rust appears.
Les résultats sont consignés dans le tableau II.
On constate que le fait d'utiliser dans le bain de conversion une concentration supérieure à 20 g/l d'ion citrate apporte un gain significatif sur le plan de la résistance à la corrosion, même sur un acier difficile à traiter comme un acier cémenté HRC 55.It is found that the fact of using in the conversion bath a concentration greater than 20 g / l of citrate ion brings a significant gain in terms of corrosion resistance, even on a steel which is difficult to treat like a case hardened steel. HRC 55.
On prépare un bain aqueux contenant (en poids/ volume):
- 25 g/l d'acide citrique
- 10 g/l d'ion NO₃
- 16,7 g/l d'ion PO₄
- 1 g/l d'ion Fe⁺⁺
- 6 g/l d'ion Zn⁺⁺
- 1 g/l d'ion Mn⁺⁺.
- 25 g / l citric acid
- 10 g / l NO₃ ion
- 16.7 g / l PO₄ ion
- 1 g / l of Fe⁺⁺ ion
- 6 g / l of Zn⁺⁺ ion
- 1 g / l of Mn⁺⁺ ion.
On chauffe le bain à 95°C et on amène l'acidité libre à une valeur de 20 points avec de la soude.The bath is heated to 95 ° C. and the free acidity is brought to a value of 20 points with sodium hydroxide.
On traite des tôles en acier laminé à froid du type ZES selon une séquence identique à celle décrite dans l'exemple 1 (l'étape de conversion mettant en oeuvre le susdit bain), à l'exception des étapes 3 et 4 qui sont supprimées. Après traitement, les tôles sont testées à l'épreuve du brouillard salin (selon ASTM B-117) et, après une exposition de 400 h, on n'observe aucun développement de rouille.Cold rolled steel sheets of the ZES type are treated in a sequence identical to that described in Example 1 (the conversion step using the above-mentioned bath), with the exception of steps 3 and 4 which are omitted . After treatment, the sheets are tested in a salt spray test (according to ASTM B-117) and, after an exposure of 400 h, no development of rust is observed.
Claims (2)
- Process for the chemical conversion characterized by the fact that it comprises the use, at the moment of the phosphatization step proper, of a zinc conversion bath free of chlorate ions and having a temperature from 70 to 99°c, the said bath containing from 0.5 to 25 g/l of zinc ion, from 5 to 40 g/l of phosphate ions, from 2 to 40 g/l of nitrate ions as well as from 0.1 to 15 g/l of iron ions and from 21 to 100 g/l of at least one organic chelating agent consisting of a polycarboxylic acid selected from the group comprising oxalic acid, malic acid, glutamic acid, tartaric acid, aspartic acid, malonic acid and citric acid, or one of its salts.
- Process according to claim 1, characterized by the fact that the bath used comprises:- from 5 to 20 g/l of phosphate ions- from 21 to 60 g/l of citric ions- from 2 to 40 g/l of nitrate ions- from 2 to 10 g/l of zinc ions- from 0,1 to 15 g/l of iron ions.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8915042 | 1989-11-16 | ||
FR8915042A FR2654440B1 (en) | 1989-11-16 | 1989-11-16 | PROCESS FOR THE CHEMICAL CONVERSION OF METAL SUBSTRATES, BATH USED IN THIS PROCESS AND CONCENTRATE FOR THE PREPARATION OF THE BATH. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0433118A1 EP0433118A1 (en) | 1991-06-19 |
EP0433118B1 true EP0433118B1 (en) | 1996-01-10 |
Family
ID=9387459
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90403233A Expired - Lifetime EP0433118B1 (en) | 1989-11-16 | 1990-11-15 | Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0433118B1 (en) |
JP (1) | JPH0730454B2 (en) |
AT (1) | ATE132917T1 (en) |
CA (1) | CA2030126C (en) |
DE (1) | DE69024774T2 (en) |
ES (1) | ES2084680T3 (en) |
FR (1) | FR2654440B1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2968127B2 (en) * | 1992-04-24 | 1999-10-25 | 日本パーカライジング株式会社 | Acid displacement plating solution for zinc or galvanized steel sheet |
JP2968147B2 (en) * | 1993-04-07 | 1999-10-25 | 日本パーカライジング株式会社 | Acid displacement plating solution composition for zinc-containing metal plated steel sheet |
DE19733972A1 (en) * | 1997-08-06 | 1999-02-11 | Henkel Kgaa | Alkaline band passivation |
EP1875003B1 (en) * | 2005-04-06 | 2013-03-06 | REM Technologies, Inc. | Superfinishing of high density carbide steel components |
JP4845050B2 (en) * | 2007-10-04 | 2011-12-28 | ユケン工業株式会社 | Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability |
JP5225466B2 (en) * | 2009-12-07 | 2013-07-03 | 新日鐵住金株式会社 | Chromate-free precoated steel plate with excellent red rust corrosion resistance |
WO2014039541A1 (en) * | 2012-09-05 | 2014-03-13 | North American Salt Company | Methods and compositions to prevent caking of sodium chloride and prevent transition metal stains |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1243081A (en) * | 1958-11-28 | 1960-10-07 | Parker Ste Continentale | Process for the phosphating of metals, in particular ferrous metals |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE975008C (en) * | 1952-08-06 | 1961-08-03 | American Chem Paint Co | Process for the production of phosphate coatings on zinc and its alloys |
US3116178A (en) * | 1961-05-29 | 1963-12-31 | Lubrizol Corp | Phosphating solutions |
BE635970A (en) * | 1962-11-13 | |||
FR1585660A (en) * | 1967-10-18 | 1970-01-30 | ||
US3767476A (en) * | 1971-08-31 | 1973-10-23 | Us Army | Method and composition for phosphatizing steel under pressure |
SU1090761A1 (en) * | 1982-07-19 | 1984-05-07 | Московский Ордена Трудового Красного Знамени Вечерний Металлургический Институт | Solution for catodic application of protective films to titanium alloys |
DE3927613A1 (en) * | 1989-08-22 | 1991-02-28 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
-
1989
- 1989-11-16 FR FR8915042A patent/FR2654440B1/en not_active Expired - Fee Related
-
1990
- 1990-11-15 AT AT90403233T patent/ATE132917T1/en not_active IP Right Cessation
- 1990-11-15 DE DE69024774T patent/DE69024774T2/en not_active Expired - Fee Related
- 1990-11-15 ES ES90403233T patent/ES2084680T3/en not_active Expired - Lifetime
- 1990-11-15 EP EP90403233A patent/EP0433118B1/en not_active Expired - Lifetime
- 1990-11-16 JP JP2308953A patent/JPH0730454B2/en not_active Expired - Lifetime
- 1990-11-16 CA CA002030126A patent/CA2030126C/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1243081A (en) * | 1958-11-28 | 1960-10-07 | Parker Ste Continentale | Process for the phosphating of metals, in particular ferrous metals |
Also Published As
Publication number | Publication date |
---|---|
DE69024774D1 (en) | 1996-02-22 |
ATE132917T1 (en) | 1996-01-15 |
CA2030126C (en) | 1999-05-11 |
DE69024774T2 (en) | 1996-07-04 |
ES2084680T3 (en) | 1996-05-16 |
EP0433118A1 (en) | 1991-06-19 |
CA2030126A1 (en) | 1991-05-17 |
FR2654440B1 (en) | 1993-07-30 |
JPH0730454B2 (en) | 1995-04-05 |
JPH03173778A (en) | 1991-07-29 |
FR2654440A1 (en) | 1991-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5089349A (en) | Compositions and method for applying coatings to metallic surfaces | |
EP0175606B1 (en) | Process for the chemical-conversion treatment of zinc or its alloys, concentrate and bath for performing this process | |
CZ281471B6 (en) | Phosphatizing process of metallic surfaces | |
EP0433118B1 (en) | Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath | |
FR2512840A1 (en) | AQUEOUS ACID SOLUTIONS FOR ZINC PHOSPHATE COATINGS AND CONCENTRATES, METHODS OF COATING THEM USING THEM AND METAL ACTIVATION SOLUTIONS USED IN SUCH PROCESSES | |
DE102005047424A1 (en) | Phosphating solution used as a pre-treatment for metal surfaces contains zinc irons, phosphate ions, hydrogen peroxide or an equivalent amount of a hydrogen peroxide-splitting substance and aliphatic chelate-forming carboxylic acid | |
JP2845246B2 (en) | Method of forming phosphate film | |
GB2203453A (en) | Phosphate coating solutions and processes | |
KR20100102619A (en) | Zirconium phosphating of metal components, in particular iron | |
JP2000516999A (en) | Aqueous solution and method for phosphating metal surfaces | |
US5045130A (en) | Solution and process for combined phosphatization | |
GB2074611A (en) | Phosphating Compositions | |
FR2502645A1 (en) | PROCESS AND COMPOSITION FOR TREATING PHOSPHATE METAL SURFACES | |
US4249964A (en) | Process for the chemical and thermal treatment of steel parts to improve the strength properties thereof | |
JPH06228766A (en) | Method of forming phosphate film | |
US4231812A (en) | Surface treatment of metal strip | |
JPS63286585A (en) | Chemical treating solution for titanium or alloy thereof and surface treatment of titanium or alloy thereof with said solution | |
EP0085626B1 (en) | Composition and process for treating phosphated metallic surfaces | |
US6168674B1 (en) | Process of phosphatizing metal surfaces | |
US5932292A (en) | Zinc phosphate conversion coating composition and process | |
EP0187597B1 (en) | Composition and process for coating metal surfaces with a conversion coating of zinc phosphate | |
BE894432A (en) | AQUEOUS COATING SOLUTIONS, ACIDS, ZINC PHOSPHATE, CONCENTRATES FOR MAKING THE SAME, ACTIVATION SOLUTIONS AND PROCESSES FOR THEIR IMPLEMENTATION | |
CN118756127A (en) | Phosphating treatment method for improving surface quality of bearing part | |
SU954518A1 (en) | Method for preparing surfaces of sliding-contact bearing parts | |
JPH01127082A (en) | Painting method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19910606 |
|
17Q | First examination report despatched |
Effective date: 19920408 |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE ES GB IT NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19960110 Ref country code: AT Effective date: 19960110 |
|
REF | Corresponds to: |
Ref document number: 132917 Country of ref document: AT Date of ref document: 19960115 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 69024774 Country of ref document: DE Date of ref document: 19960222 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19960305 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19960410 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2084680 Country of ref document: ES Kind code of ref document: T3 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19970128 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19971029 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19971130 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19980127 Year of fee payment: 8 |
|
BERE | Be: lapsed |
Owner name: CIE FRANCAISE DE PRODUITS INDUSTRIELS Effective date: 19971130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981115 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19981207 Year of fee payment: 9 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19981115 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991116 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20001214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051115 |