EP0751239A1 - Procédé de remontage de solution de phosphatation - Google Patents

Procédé de remontage de solution de phosphatation Download PDF

Info

Publication number: EP0751239A1
Authority: EP; European Patent Office
Prior art keywords: phosphating; zinc; phosphating solutions; contain; solutions
Prior art date: 1995-06-30
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 Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn

Application number

EP96109549A

Other languages

German (de)

English (en)

Inventor

Horst Dr. Gehmecker

Thomas Kolberg

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

GEA Group AG

Original Assignee

Metallgesellschaft AG

Priority date (The priority date 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 date listed.)

1995-06-30

Filing date

1996-06-14

Publication date

1997-01-02

1996-06-14 Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG

1997-01-02 Publication of EP0751239A1 publication Critical patent/EP0751239A1/fr

Status Withdrawn legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims description 26
230000003716 rejuvenation Effects 0.000 title 1
229920001222 biopolymer Polymers 0.000 claims abstract description 14
229910000831 Steel Inorganic materials 0.000 claims abstract description 10
239000010959 steel Substances 0.000 claims abstract description 10
239000000654 additive Substances 0.000 claims abstract description 8
229910052751 metal Inorganic materials 0.000 claims abstract description 7
239000002184 metal Substances 0.000 claims abstract description 7
150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 6
150000002739 metals Chemical class 0.000 claims abstract description 5
229920001817 Agar Polymers 0.000 claims abstract description 3
229920000945 Amylopectin Polymers 0.000 claims abstract description 3
229920000856 Amylose Polymers 0.000 claims abstract description 3
229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 3
229920001202 Inulin Polymers 0.000 claims abstract description 3
229920002472 Starch Polymers 0.000 claims abstract description 3
150000001720 carbohydrates Chemical class 0.000 claims abstract description 3
235000014633 carbohydrates Nutrition 0.000 claims abstract description 3
150000004676 glycans Chemical class 0.000 claims abstract description 3
JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims abstract description 3
229940029339 inulin Drugs 0.000 claims abstract description 3
229920001282 polysaccharide Polymers 0.000 claims abstract description 3
239000005017 polysaccharide Substances 0.000 claims abstract description 3
235000019698 starch Nutrition 0.000 claims abstract description 3
229910052725 zinc Inorganic materials 0.000 claims description 24
239000011701 zinc Substances 0.000 claims description 24
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
229910019142 PO4 Inorganic materials 0.000 claims description 14
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
239000010452 phosphate Substances 0.000 claims description 12
239000013589 supplement Substances 0.000 claims description 11
229910052782 aluminium Inorganic materials 0.000 claims description 9
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
238000000576 coating method Methods 0.000 claims description 9
150000007514 bases Chemical class 0.000 claims description 7
229910052759 nickel Inorganic materials 0.000 claims description 7
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 6
229910000165 zinc phosphate Inorganic materials 0.000 claims description 6
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
229910052802 copper Inorganic materials 0.000 claims description 5
239000010949 copper Substances 0.000 claims description 5
238000005516 engineering process Methods 0.000 claims description 5
150000004679 hydroxides Chemical class 0.000 claims description 5
229910052749 magnesium Inorganic materials 0.000 claims description 5
239000011777 magnesium Substances 0.000 claims description 5
150000002978 peroxides Chemical class 0.000 claims description 5
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 claims description 4
229910017052 cobalt Inorganic materials 0.000 claims description 3
239000010941 cobalt Substances 0.000 claims description 3
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
230000009469 supplementation Effects 0.000 claims description 3
239000008272 agar Substances 0.000 claims description 2
239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
238000004519 manufacturing process Methods 0.000 claims description 2
239000008107 starch Substances 0.000 claims description 2
230000000996 additive effect Effects 0.000 abstract 2
241000206672 Gelidium Species 0.000 abstract 1
235000010419 agar Nutrition 0.000 abstract 1
229920006184 cellulose methylcellulose Polymers 0.000 abstract 1
235000021317 phosphate Nutrition 0.000 description 13
239000007787 solid Substances 0.000 description 7
MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
230000015572 biosynthetic process Effects 0.000 description 6
239000012141 concentrate Substances 0.000 description 6
238000007792 addition Methods 0.000 description 5
239000003795 chemical substances by application Substances 0.000 description 5
230000003472 neutralizing effect Effects 0.000 description 5
XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
239000002253 acid Substances 0.000 description 4
150000002500 ions Chemical class 0.000 description 4
238000010422 painting Methods 0.000 description 4
229910001335 Galvanized steel Inorganic materials 0.000 description 3
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 3
239000008397 galvanized steel Substances 0.000 description 3
229910052742 iron Inorganic materials 0.000 description 3
229910052748 manganese Inorganic materials 0.000 description 3
239000011572 manganese Substances 0.000 description 3
239000000463 material Substances 0.000 description 3
239000000203 mixture Substances 0.000 description 3
230000000087 stabilizing effect Effects 0.000 description 3
239000011667 zinc carbonate Substances 0.000 description 3
229910000010 zinc carbonate Inorganic materials 0.000 description 3
235000004416 zinc carbonate Nutrition 0.000 description 3
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
229910002651 NO3 Inorganic materials 0.000 description 2
NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
229910001297 Zn alloy Inorganic materials 0.000 description 2
239000000956 alloy Substances 0.000 description 2
-1 ammonium ions Chemical class 0.000 description 2
SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
229910052791 calcium Inorganic materials 0.000 description 2
239000011575 calcium Substances 0.000 description 2
AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
239000000920 calcium hydroxide Substances 0.000 description 2
229910001861 calcium hydroxide Inorganic materials 0.000 description 2
238000004140 cleaning Methods 0.000 description 2
239000011248 coating agent Substances 0.000 description 2
150000001875 compounds Chemical class 0.000 description 2
238000001704 evaporation Methods 0.000 description 2
230000008020 evaporation Effects 0.000 description 2
150000002222 fluorine compounds Chemical class 0.000 description 2
239000007789 gas Substances 0.000 description 2
238000010438 heat treatment Methods 0.000 description 2
229910052739 hydrogen Inorganic materials 0.000 description 2
CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
239000008237 rinsing water Substances 0.000 description 2
239000007921 spray Substances 0.000 description 2
238000005507 spraying Methods 0.000 description 2
230000000153 supplemental effect Effects 0.000 description 2
230000001502 supplementing effect Effects 0.000 description 2
IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 description 1
229910000851 Alloy steel Inorganic materials 0.000 description 1
VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
229910000611 Zinc aluminium Inorganic materials 0.000 description 1
230000002730 additional effect Effects 0.000 description 1
239000003513 alkali Substances 0.000 description 1
229910045601 alloy Inorganic materials 0.000 description 1
HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
239000000908 ammonium hydroxide Substances 0.000 description 1
150000001450 anions Chemical class 0.000 description 1
239000007900 aqueous suspension Substances 0.000 description 1
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
229910052788 barium Inorganic materials 0.000 description 1
DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
239000002585 base Substances 0.000 description 1
SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
229910052793 cadmium Inorganic materials 0.000 description 1
BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
229940043430 calcium compound Drugs 0.000 description 1
150000001674 calcium compounds Chemical class 0.000 description 1
BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
238000007598 dipping method Methods 0.000 description 1
239000006185 dispersion Substances 0.000 description 1
238000004070 electrodeposition Methods 0.000 description 1
CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
239000007788 liquid Substances 0.000 description 1
238000002156 mixing Methods 0.000 description 1
238000006386 neutralization reaction Methods 0.000 description 1
QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
150000002828 nitro derivatives Chemical class 0.000 description 1
GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
239000001301 oxygen Substances 0.000 description 1
229910052760 oxygen Inorganic materials 0.000 description 1
238000005191 phase separation Methods 0.000 description 1
239000000843 powder Substances 0.000 description 1
238000010433 powder painting Methods 0.000 description 1
230000001376 precipitating effect Effects 0.000 description 1
238000005086 pumping Methods 0.000 description 1
238000007670 refining Methods 0.000 description 1
238000004062 sedimentation Methods 0.000 description 1
238000005204 segregation Methods 0.000 description 1
229910052710 silicon Inorganic materials 0.000 description 1
239000010703 silicon Substances 0.000 description 1
229910000029 sodium carbonate Inorganic materials 0.000 description 1
238000003756 stirring Methods 0.000 description 1
238000003860 storage Methods 0.000 description 1
239000000126 substance Substances 0.000 description 1
239000000725 suspension Substances 0.000 description 1
PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
239000002699 waste material Substances 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds

Definitions

the invention relates to a method for supplementing phosphating solutions for producing phosphate coatings on surfaces of steel, zinc and / or aluminum with the aid of aqueous supplements which are poorly water-soluble basic compounds selected from the group of oxides, hydroxides and / or carbonates of phosphating agents Contain metals, as well as its application to the addition of zinc phosphate solutions working in particular according to the low zinc technology, preferably with peroxide as accelerator.
aqueous supplements which are poorly water-soluble basic compounds selected from the group of oxides, hydroxides and / or carbonates of phosphating agents Contain metals
phosphating solutions used for this usually contain zinc and phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, m-nitrobenzenesulfonate, nitrophenol or combinations thereof, possibly also nickel, manganese, magnesium, cadmium, Copper, cobalt, calcium, alkali and / or ammonium ions.
the solution additionally contains iron (II) ions.
the phosphating solutions preferably contain simple and / or complex fluorides. Anions, such as chloride and sulfate, serve to maintain electroneutrality. If necessary, the phosphating solutions can also contain layer-refining additives such as hydroxycarboxylic acids, aminocarboxylic acids or condensed phosphates.
the object of the invention is to provide a method for supplementing phosphating solutions for producing phosphate coatings on surfaces of steel, zinc and / or aluminum with the aid of aqueous supplements, which does not have the disadvantages of the known, in particular the aforementioned methods, can be carried out simply and inexpensively is and in particular enables a precise dosage of the supplementary chemicals.
the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that aqueous phosphates which contain biopolymer to stabilize the sparingly soluble basic compounds are added to the phosphating solutions.
the process according to the invention can be used in practically all phosphating processes, i.e. in processes that work with solutions based on zinc phosphate, modified phosphating solutions based on zinc phosphate and with phosphating solutions based on manganese phosphate.
the phosphating solutions can be run on the iron side or be iron-free.
Modified phosphating solutions based on zinc phosphate are understood to be those which belong to the normal zinc or low zinc technology and which e.g. are modified by additions of nickel, manganese, magnesium, calcium, barium, copper and / or simple or complex fluorides and tungstate.
the method according to the invention is applicable to the phosphating of surfaces made of steel, zinc and / or aluminum.
the steels can be unalloyed or low-alloyed.
the zinc surface can come from workpieces made of solid zinc or solid zinc alloys or galvanized material. The latter include workpieces that have been coated with zinc or zinc alloy coatings, such as pure zinc, zinc-nickel, zinc-iron, zinc-aluminum, for example by hot-dip or electrolytic processes.
Aluminum in the sense of the invention includes, among other things, pure aluminum and alloys of aluminum with magnesium, zinc, copper, silicon, manganese etc. or materials coated with it.
Supplements are preferably added to the phosphating solutions which contain oxides, hydroxides and / or carbonates of the metals zinc, manganese, nickel, cobalt, copper and / or magnesium as basic compounds.
the biopolymers In addition to stabilizing the poorly soluble, basic compounds in the supplement, the biopolymers have the additional effect that they are introduced into the phosphating solution via the supplement in the phosphating systems, in particular in pipelines, nozzles and heating units, which usually significantly reduce the inevitable crust formation.
This additional advantage is significant insofar as, for example in spraying systems, the flow of the phosphating solution is reduced by crust formation, so that satisfactory formation of the phosphate layer can be disturbed as a result of changed spraying conditions.
the incrustation on heating elements results in insufficient heat transfer and thus problems in maintaining the temperature constancy in the phosphating bath, which in turn generally affects the quality of the phosphate layer formed.
a preferred embodiment of the invention provides for the phosphating solution to be supplemented with supplements which contain, as biopolymers, carbohydrates or polysaccharides such as starch, amylose, amylopectin, inulin, agar and carboxymethyl cellulose. These compounds are distinguished by the fact that they impart particularly high transport and storage stability to the supplement concentrates and are particularly effective in preventing crust formation.
the phosphating solution is supplemented which contain the biopolymer in a concentration of 0.1 to 5% by weight, preferably 0.3 to 1.5% by weight.
concentrations below the lower limit the stabilizing effect of the biopolymer may not be sufficient to ensure that the dispersion is homogenized sufficiently. Concentrations above the upper limit bring practically no additional improvement in the stabilizing effect.
the process according to the invention is particularly advantageously applicable to the supplementation of phosphating solutions based on zinc phosphate, in particular of phosphating processes working in accordance with the low zinc technology, since the additives usually used in these processes, such as nitrate, chlorate, peroxide, hydroxylammonium compounds or organic nitro compounds, none or none have sufficient alkaline character. It does not matter whether the processes are iron-free or on the iron side.
phosphating solutions are to be supplemented which contain only those components which are consumed in the formation of the phosphate layer or which can be precipitated with calcium compounds, in particular calcium hydroxide.
phosphating solutions there is the possibility of precipitating foreign ions from rinsing water obtained in rinsing stages and reusing the rinsing water for rinsing purposes or adding phosphating solutions to cover evaporation losses without undesirable ions thereby getting into the phosphating solution.
Phosphating solutions of the aforementioned type usually work with peroxides, in particular hydrogen peroxide, possibly together with oxygen-containing gases or nitrous gases as accelerators.
a phosphating solution accelerated with hydrogen peroxide of the following composition was used for zinc phosphating in the dipping process of metal surfaces which consisted of 80% steel and 20% galvanized steel: 1.4 g / l zinc Free acid 1.4 pts. 1.0 g / l manganese Total acidity 25 pts. 1.0 g / l nickel S value 0.10 13.0 g / l phosphate (calculated as P 2 O 5 ) 25.0 mg / l H 2 O 2
the solution was applied at a temperature of 58 +/- 2 ° C for a period of 3.5 min.
the bathroom components that used up during the material throughput were supplemented with three supplementary solutions.
the composition of the solutions was as follows (each stated in% by weight): Solution 1 (supplemental concentrate) Solution 2 (neutralizing agent) Solution 3 (accelerator) 5.0% Zn 13.5% bas. Zinc carbonate 35% H 2 O 2 1.3% Ni 0.7% biopolymer 1.7% Mn 23.4% P 2 O 5
a zinc phosphating solution of 100% steel in a spray process was accelerated with a phosphating solution accelerated with hydrogen peroxide with the following composition: 2.8 g / l zinc Free acidity 0.8 pts. 0.22 g / l approx Total acidity 15 pts. 0.01 g / l Ni S value 0.08 7.7 g / l P 2 O 5 70 mg / l H 2 O 2

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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)
Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

EP96109549A 1995-06-30 1996-06-14 Procédé de remontage de solution de phosphatation Withdrawn EP0751239A1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE1995123919 DE19523919A1 (de)	1995-06-30	1995-06-30	Verfahren zur Ergänzung von Phosphatierungslösung
DE19523919		1995-06-30

Publications (1)

Publication Number	Publication Date
EP0751239A1 true EP0751239A1 (fr)	1997-01-02

Family

ID=7765723

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP96109549A Withdrawn EP0751239A1 (fr)	1995-06-30	1996-06-14	Procédé de remontage de solution de phosphatation

Country Status (4)

Country	Link
EP (1)	EP0751239A1 (fr)
CN (1)	CN1151448A (fr)
CA (1)	CA2180169A1 (fr)
DE (1)	DE19523919A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CN100392149C (zh) *	2006-05-18	2008-06-04	武汉理工大学	含可溶性淀粉的磷化液及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB858960A (en) *	1958-09-18	1961-01-18	Ici Ltd	Improvements in or relating to phosphate coating processes
FR2022052A1 (fr) *	1968-10-31	1970-07-24	Hooker Chemical Corp
US3723334A (en) *	1971-10-26	1973-03-27	Oxy Metal Finishing Corp	Scale reducing agent in zinc phosphatizing compositions
FR2231775A1 (en) *	1973-05-29	1974-12-27	Parker Ste Continentale	Phosphate-coating solns. - free from formation of water-soluble salts during neutralization
FR2401235A1 (fr) *	1977-08-25	1979-03-23	Parker Ste Continentale	Procede de phosphatation au zinc accelere par du peroxyde
EP0414301A1 (fr) *	1989-08-22	1991-02-27	METALLGESELLSCHAFT Aktiengesellschaft	Procédé d'obtention de revêtement de phosphate sur des surfaces métalliques
EP0414296A1 (fr) *	1989-08-22	1991-02-27	METALLGESELLSCHAFT Aktiengesellschaft	Procédé d'obtention de revêtements de phosphates sur des surfaces métalliques
US5378292A (en) *	1993-12-15	1995-01-03	Henkel Corporation	Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator

1995
- 1995-06-30 DE DE1995123919 patent/DE19523919A1/de not_active Withdrawn
1996
- 1996-06-14 EP EP96109549A patent/EP0751239A1/fr not_active Withdrawn
- 1996-06-27 CA CA 2180169 patent/CA2180169A1/fr not_active Abandoned
- 1996-06-28 CN CN 96110140 patent/CN1151448A/zh active Pending

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB858960A (en) *	1958-09-18	1961-01-18	Ici Ltd	Improvements in or relating to phosphate coating processes
FR2022052A1 (fr) *	1968-10-31	1970-07-24	Hooker Chemical Corp
US3723334A (en) *	1971-10-26	1973-03-27	Oxy Metal Finishing Corp	Scale reducing agent in zinc phosphatizing compositions
FR2231775A1 (en) *	1973-05-29	1974-12-27	Parker Ste Continentale	Phosphate-coating solns. - free from formation of water-soluble salts during neutralization
FR2401235A1 (fr) *	1977-08-25	1979-03-23	Parker Ste Continentale	Procede de phosphatation au zinc accelere par du peroxyde
EP0414301A1 (fr) *	1989-08-22	1991-02-27	METALLGESELLSCHAFT Aktiengesellschaft	Procédé d'obtention de revêtement de phosphate sur des surfaces métalliques
EP0414296A1 (fr) *	1989-08-22	1991-02-27	METALLGESELLSCHAFT Aktiengesellschaft	Procédé d'obtention de revêtements de phosphates sur des surfaces métalliques
DE3927613A1 (de) *	1989-08-22	1991-02-28	Metallgesellschaft Ag	Verfahren zur erzeugung von phosphatueberzuegen auf metalloberflaechen
DE3927614A1 (de) *	1989-08-22	1991-02-28	Metallgesellschaft Ag	Verfahren zur erzeugung von phosphatueberzuegen auf metallen
US5378292A (en) *	1993-12-15	1995-01-03	Henkel Corporation	Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator

Also Published As

Publication number	Publication date
CA2180169A1 (fr)	1996-12-31
CN1151448A (zh)	1997-06-11
DE19523919A1 (de)	1997-01-02

Publication	Publication Date	Title
EP0459541B1 (fr)	1995-11-22	Procédé de phosphatation de surfaces métalliques
EP0064790A1 (fr)	1982-11-17	Procédé pour la phosphatation de métaux ainsi que son utilisation pour le prétraitement pour la peinture électrique au trempé
DE2845439A1 (de)	1979-04-26	Verfahren zur stabilisierung galvanischer baeder bei der herstellung von ueberzuegen aus zinn oder zinnlegierungen
DE861184C (de)	1952-12-29	Verfahren zur Bildung von UEberzuegen auf rostfreien Staehlen
EP0478648B1 (fr)	1995-01-18	Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium
EP0717787B1 (fr)	1998-01-14	Procede de phosphatage sans nickel
DD299661A5 (de)	1992-04-30	Verfahren zur erzeugung von phosphatueberzuegen auf metalloberflaechen
EP0370535B1 (fr)	1992-11-11	Procédé pour appliquer des revêtements de phosphate
DE3902266A1 (de)	1989-08-17	Verfahren zum aufbringen von konversionsueberzuegen
DE2538347C3 (de)	1981-10-08	Zinkphosphatlösungen zur Ausbildung von Zinkphosphatschichten auf Metallen
EP0134895B1 (fr)	1988-11-30	Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques
DE2327304B2 (de)	1981-02-26	Verfahren zum Aufbringen von Phosphatüberzügen auf Metalle
EP1060290B1 (fr)	2002-09-18	Solution aqueuse et procede pour phosphater des surfaces metalliques
EP0059994B1 (fr)	1984-12-27	Procédé pour la fabrication de révêtements de phosphate sur des sufaces métalliques
DE3780078T2 (de)	1992-12-24	Korrosionsbestaendige beschichtung.
EP0121274A1 (fr)	1984-10-10	Procédé de phosphatation de surfaces métalliques
EP0751239A1 (fr)	1997-01-02	Procédé de remontage de solution de phosphatation
WO1999045171A1 (fr)	1999-09-10	Commande de poids de couche lors de la phosphatation d'une bande
EP0866888B1 (fr)	1999-06-16	Procede pour la phosphatation de surfaces metalliques
WO1993022474A1 (fr)	1993-11-11	Procede de phosphatation sans nickel avec du cuivre
DE1184590B (de)	1964-12-31	Verfahren zum Aufbringen von Phosphatueberzuegen auf metallischen Oberflaechen
DE2738281A1 (de)	1979-03-01	Verfahren zur phosphatierung von metallen
DE2239813C3 (de)	1980-11-06	Verfahren zur Ergänzung einer Zinkphosphat und Chlorat enthaltenden Lösung für die Spritzphosphatierung
DE2213781B2 (de)	1977-03-17	Verfahren zur phosphatierung von stahl
DE2738283A1 (de)	1979-03-01	Verfahren zur phosphatierung von metallen

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