EP0596273B1 - Produits de décapage de surfaces d'aciers au chromenickel ou d'aciers du chrome et leur utilisation - Google Patents
Produits de décapage de surfaces d'aciers au chromenickel ou d'aciers du chrome et leur utilisation Download PDFInfo
- Publication number
- EP0596273B1 EP0596273B1 EP93116251A EP93116251A EP0596273B1 EP 0596273 B1 EP0596273 B1 EP 0596273B1 EP 93116251 A EP93116251 A EP 93116251A EP 93116251 A EP93116251 A EP 93116251A EP 0596273 B1 EP0596273 B1 EP 0596273B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- chromium
- weight
- pickling
- composition according
- 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
- 238000005554 pickling Methods 0.000 title claims abstract description 33
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 21
- 239000010959 steel Substances 0.000 title claims abstract description 21
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 title description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 Fe(III) ions Chemical class 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 10
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 11
- 239000003086 colorant Substances 0.000 abstract description 3
- 238000005494 tarnishing Methods 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract 1
- 235000021110 pickles Nutrition 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000669 Chrome steel Inorganic materials 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000834 fixative Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 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 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KVUUQMDVROTSNI-UHFFFAOYSA-N [morpholin-4-yl(phosphono)methyl]phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)N1CCOCC1 KVUUQMDVROTSNI-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/06—Wholly-metallic mirrors
Definitions
- the invention relates to a means for pickling the surface of Chromium-nickel steels and chromium steels, which sulfuric acid, Contains phosphoric acid or mixtures thereof and Fe (III) ions. Furthermore, the invention relates to the use of a corresponding By means of an electrochemical and / or chemical Process for pickling the surface of stainless steel or Nickel steels.
- Pickling and cleaning agents known in the prior art for Chromium-nickel and chromium steels usually contain an active one Acid and an inhibiting or oxidizing component.
- active components get sulfuric acid, hydrochloric acid and / or Hydrofluoric acid used.
- inhibiting or oxidizing Component usually serves nitric acid.
- the pickling process serves, among other things, to remove impurities to be eliminated by foreign metals (e.g. ferrite contamination). It is also a result of heat treatment or scaling or tarnishing colors created during welding as well fix organic contaminants and a metallic one to create pure surface. This is the requirement for the fact that the chromium content of the alloy and the surrounding oxygen a closed, corrosion-resistant Form a chromium oxide layer on the workpiece surface can. Only this forms the basis for the desired one Corrosion resistance of the materials.
- Pickling agents according to the prior art generally contain Hydrofluoric acid as an active component and nitric acid as an oxidizing component.
- the nitric acid also inhibits the attack the hydrofluoric acid on the metal surface, so that this Attack mainly on the oxides and metallic contaminants aligns and thus promotes the dissolution of the oxides becomes.
- EP-A-0 501 867 discloses a method for the treatment of Steels, in which the pickling agent components include Sulfuric acid or phosphoric acid together with iron ions be proposed. The process comes first the redox potential of the treatment bath on one hold certain value. According to the only embodiment is called hydrogen fluoride with a concentration of 80 g / l used.
- a process for pickling stainless steel is known from EP-A-0 505 606, in which, in addition to sulfuric acid and iron 3+ ions, the HF concentration must be at least 40 g / l. H 2 O 2 is also required as the oxidizing agent. Finally, the redox potential of the treatment solution must also be kept at a certain value in this process.
- a pickling agent is known from US Pat. No. 3,785,866, which is particularly suitable for pickling zinc surfaces.
- this mordant may contain fluoroboric acid as the proton-providing source.
- such a mordant can contain iron (III) sulfate, fluoroboric acid and sulfuric acid.
- certain additives such as sodium fluoroborate or ammonium fluoroborate, can be added to a pickling agent for chromium-containing steels which contains 20-400 g / l sulfuric acid.
- a method for pickling stainless steel is known from US Pat. No. 3,010,854, a solution comprising nitric acid, phosphoric acid and fluorosilicates being used. The fluorosilicates can also be replaced by HBF 4 .
- the problem of the present invention is a Means for pickling and / or cleaning the surfaces of stainless steel and provide chrome steels that reduce environmental pollution and hazards from those in the prior art avoid known agents with nitric acid and hydrofluoric acid or reduced.
- Such a means should also meet the requirements for such Means for cleaning and pickling are sufficient.
- it depends on the effect of the agent largely on the undesirable oxide deposits and impurities judges.
- the appearance and structure of the metallic At the same time, the surface should be largely preserved stay.
- nitric acid and Hydrofluoric acid can be completely dispensed with.
- the agents according to the invention preferably contain the Fe (III) ions in the form of their water-soluble salts with a concentration up to 5% by weight, preferably 0.5 to 3% by weight.
- Suitable water-soluble salts are iron (III) sulfate, Iron (III) citrate or iron (III) acetylacetonate.
- the fluoroboric acid has a concentration in aqueous solution proven from 0.1 to 5.0 wt .-%. It was surprisingly found that by means of fluoroboric acid a faster and more thorough pickling effect is achieved than with fluorosilicic acid.
- the agents according to the invention can but also hydrofluoric acid (HF) in a concentration of up to 0.5 % By weight, preferably 0.2 to 0.4% by weight.
- HF hydrofluoric acid
- the Hydrofluoric acid is used here only in very low concentrations the disadvantages of the prior art do not occur to the same extent as there. But in particular there is none Addition of nitric acid required. The product is therefore non-toxic in accordance with the Ordinance on Hazardous Substances.
- the agent usually contains pickling and / or cleaning of metal surfaces an acid or acids and their mixtures in concentrations of 2 to 70% by weight, preferably from 15 to 35% by weight.
- These acids in addition to sulfuric acid especially phosphoric acid and amidosulfonic acid serve essentially for dissolving tarnishing colors in heat affected zones and scale layers in the weld area.
- inorganic and / or organic acids can be used in the agents according to the invention.
- An effective improvement of the agents has been shown if additionally 0.1 to 30% by weight of substituted or unsubstituted carboxylic acids with 1 to 6 carbon atoms or polycarboxylic acids are used. Of these acids, 0.1 to 10% by weight are preferably used.
- the substituted and unsubstituted carboxylic acids with 1 to 6 carbon atoms are, for example: Citric acid, oxalic acid, formic acid, gluconic acid, maleic acid, tartaric acid, acetic acid, propanoic acid, etc.
- polycarboxylic acids such as polyacrylic acid can also be used or polymethacrylic acid are used.
- Farther can be derivatives of the abovementioned acids or polyacids are used, such as hexanoic acid diamide and succinic acid diamide and their mixtures.
- chelating agents can affect the pickling effect Improve agents according to the invention.
- a chelating agent can advantageously phosphonic acids, especially hydroxyethane-1,1-diphosphonic acid or morpholinomethane diphosphonic acid, preferred in a concentration of 0.1 to 5% by weight will.
- the agents according to the invention can contain an oxidizing agent for the oxidation of scale layers; these oxidizing agents are preferred in amounts of 1 to 3% by weight.
- an oxidizing agent for the oxidation of scale layers these oxidizing agents are preferred in amounts of 1 to 3% by weight.
- one or more nitro-substituted aromatic compounds with one or more NO 2 groups bonded to the aromatic ring nucleus in addition to a water-solubilizing group, also bonded to an aromatic nucleus, such as sodium m-nitrobenzenesulfonate or m-nitrobenzenesulfonic acid can be used.
- the agents according to the invention can moreover be the usual ones Contain amounts of surfactants.
- the agents according to the invention can be both liquid and immersion and Riesling also thickened by a suitable thickener such as barium sulfate, aerosil, lumic acid, etc as spreadable or sprayable pickling paste.
- a suitable thickener such as barium sulfate, aerosil, lumic acid, etc as spreadable or sprayable pickling paste.
- the funds work particularly good in the temperature range from 10 ° C to 80 ° C.
- Surfactants in concentrations can also be used as further constituents of 0.1-2% by weight.
- the rest (to 100 wt .-%) exists then optionally from other strong acids - at least 10% by weight, for example phosphoric acid and / or known thickeners.
- the invention furthermore relates to the use of the agent according to the invention in an electrochemical and / or chemical process for pickling surfaces of chromium-nickel steels and chromium steels. It has proven to be particularly advantageous if an anodic current density of 0.2 to 30 A / dm 2 is used in an electrochemical process.
- the method according to the invention can be used in particular for descaling of metallic surfaces are used, whereby other electrochemical treatment steps such as Can connect electropolishing.
- the invention now represents an environmentally friendly and health less dangerous agent for pickling and / or cleaning of metallic surfaces.
- As a special advantage of the agent according to the invention or the method according to the invention shows that with regard to the required pickling effect a significant reduction in the pickling time can be obtained.
- composition 2 Phosphoric acid 85% 16.0% by weight 96% sulfuric acid 32.0 " Iron (III) sulfate 1.9 " Wetting agent 0.2 " Butyl glycol 3.0 " 1-hydroxyethane-1,1-diphosphonic acid 0.5 " Sodium salt of m-nitrobenzenesulfonic acid 2.3 " Succinic acid diamide 1.0 " 100% tetrafluoroboric acid 1.7 " water 41.4 " total 100.0% by weight
- composition 3 Phosphoric acid 85% 24.0% by weight 96% sulfuric acid 18.0 " Amidosulfonic acid 3.0 " 1-hydroxyethane-1,1-diphosphonic acid 3.0 " Butyl glycol 1.0 " Sodium salt of m-nitrobenzenesulfonic acid 2.0 " Iron (III) sulfate 0.8 " 100% tetrafluoroboric acid 1.7 " water 46.3% by weight 100.0% by weight
- Stainless steel sheets as before were made with a composition treated according to DE 37 42 367 Al (Example 1).
- the stainless steel sheets 30, 60, 120 and 180 were welded Stained for minutes at 23 ° C.
- the mordant according to the prior art had the following composition. Nitric acid (100%) 18% by weight Fluorosilicic acid (100%) 6 " water 75.09 " Surfactant 0.01 " Polysaccharide 0.90 "
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Chemical Treatment Of Metals (AREA)
Claims (11)
- Produit de décapage de la surface d'aciers au chrome-nickel et d'aciers au chrome, qui contient dc l'acide sulfurique, dc l'acidc phosphorique ou leurs mélanges et des ions Fe(III),
caractérisé par le fait qu'il contient de l'acide fluoborique dans une concentration de 0,1 à 5% en poids ainsi qu'au maximum 0,5% en poids d'acide fluorhydrique, la concentration en ions (Fe(III) (calculée sous la forme sulfate de fer(III)) valant 0,5-5% en poids. - Produit selon la revendication 1,
caractérisé par le fait qu'il contient d'autres acides non organiques et/ou organiques. - Produit selon l'une des revendications précédentes,
caractérisé par le fait qu'il contient de l'acide fluorhydrique (HF) dans une concentration de 0,2 à 0,4% en poids. - Produit selon l'une des revendications précédentes,
caractérisé par le fait qu'il conticnt de 2 à 70% en poids d'acide sulfurique, d'acide phosphorique et/ou d'acide amidosulfonique. - Produit selon la revendication 1,
caractérisé par le fait qu'il contient de 0,1 à 30% en poids d'acides carboxyliques contenant de 1 à 6 atomes de carbone, ou d'acides polycarboxyliques, ayant ou non fait l'objet d'une substitution. - Produit selon l'une des revendications 1 à 5,
caractérisé par le fait qu'il contient un agent d'oxydation. - Produit selon la revendication 6,
caractérisé par le fait que comme agent d'oxydation il contient un ou plusieurs composés aromatiques ayant subi une substitution par le groupement nitro. - Produit selon l'une des revendications 1 à 7,
caractérisé par le fait qu'il contient des chélateurs. - Produit selon l'une des revendication 1 à 8,
caractérisé par le fait qu'il contient des tensides. - Emploi d'un produit selon l'une des revendications 1 à 9, dans un procédé électrochimiquc et/ou chimique pour décaper la surface d'aciers au chrome-nickel ou d'aciers au chrome.
- Emploi selon la revendication 10, dans un procédé électrochimique qui travaille avec une densité de courant anodiquc de 0,2 à 30 A/dm2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4237021A DE4237021C1 (de) | 1992-11-02 | 1992-11-02 | Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels |
| DE4237021 | 1992-11-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0596273A1 EP0596273A1 (fr) | 1994-05-11 |
| EP0596273B1 true EP0596273B1 (fr) | 1998-05-06 |
Family
ID=6471947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93116251A Expired - Lifetime EP0596273B1 (fr) | 1992-11-02 | 1993-10-07 | Produits de décapage de surfaces d'aciers au chromenickel ou d'aciers du chrome et leur utilisation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0596273B1 (fr) |
| AT (1) | ATE165876T1 (fr) |
| DE (2) | DE4237021C1 (fr) |
| DK (1) | DK0596273T3 (fr) |
| ES (1) | ES2114991T3 (fr) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9401214A (pt) * | 1994-03-18 | 1995-10-24 | Frimox Quimica Ltda | Composição,solução e processo de tratamento de superfícies de materiais ferrosos |
| DE19833990A1 (de) | 1998-07-29 | 2000-02-10 | Metallgesellschaft Ag | Beizmittel für Edelstähle |
| DE10110823A1 (de) * | 2001-03-07 | 2002-10-02 | Bosch Gmbh Robert | Verfahren zum Abtragen von Materialablagerungen, die bei einer Laserbearbeitung entstehen |
| US8192556B2 (en) | 2002-10-15 | 2012-06-05 | Henkel Kgaa | Pickling or brightening/passivating solution and process for steel and stainless steel |
| DE10341061B4 (de) * | 2003-09-05 | 2007-08-02 | Poligrat Gmbh | Elektropolierverfahren für Leichtmetalllegierungen und Elektrolyt |
| DE102005055768A1 (de) * | 2005-11-21 | 2007-05-24 | Ralf Waldmann | Verfahren und Mittel zur elektrolytischen Reinigung und Entzunderung eines metallischen Werkstücks |
| DE102007010538A1 (de) | 2007-03-05 | 2008-09-11 | Poligrat Gmbh | Verfahren zum thermochemischen Passivieren von Edelstahl |
| DE102008021299A1 (de) * | 2008-04-21 | 2009-10-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Katalysator für toxische Kohlenwasserstoffverbindungen und/oder organische Verbindungen sowie Verfahren zu seiner Herstellung |
| DE102016210289A1 (de) | 2016-06-10 | 2017-12-14 | Henkel Ag & Co. Kgaa | Verfahren zur reinigenden Vorbehandlung von durch Schweißen zusammengefügten eisenhaltigen Bauteilen |
| EP3269844A1 (fr) * | 2016-07-11 | 2018-01-17 | Beratherm AG | Solution de nettoyage aqueuse destinée à éliminer des couches de noir de fonderie sur des surfaces d'aciers inoxydables en contact avec des fluides , son utilisation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3010854A (en) * | 1954-12-31 | 1961-11-28 | Armco Steel Corp | Pickling solution and method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US947067A (en) * | 1908-09-30 | 1910-01-18 | Int Nickel Co | Method of treating nickel-copper alloys. |
| GB891670A (en) * | 1957-09-04 | 1962-03-14 | English Electric Co Ltd | Improvements in and relating to the removing of scale from silicon iron and other metals |
| US3446715A (en) * | 1965-04-09 | 1969-05-27 | Oakite Prod Inc | Metal treating |
| JPS61235581A (ja) * | 1985-04-12 | 1986-10-20 | C Uyemura & Co Ltd | スケ−ル除去剤及びスケ−ル除去方法 |
| JPS61276999A (ja) * | 1985-05-30 | 1986-12-06 | Nippon Steel Corp | Cr含有鋼板の酸洗法 |
| DE3742367A1 (de) * | 1987-12-14 | 1989-06-22 | Pelox Chemietechnik Gmbh Co Kg | Beiz- und reinigungsmittel fuer metalloberflaechen |
| JPH0273983A (ja) * | 1988-09-07 | 1990-03-13 | Nippon Parkerizing Co Ltd | アルミニウム用酸性洗浄液 |
| FR2673200A1 (fr) * | 1991-02-25 | 1992-08-28 | Ugine Aciers | Procede de surdecapage de materiaux en acier tels que les aciers inoxydables et les aciers allies. |
| IT1245594B (it) * | 1991-03-29 | 1994-09-29 | Itb Srl | Processo di decapaggio e di passivazione di acciaio inossidabile senza acido nitrico |
-
1992
- 1992-11-02 DE DE4237021A patent/DE4237021C1/de not_active Expired - Fee Related
-
1993
- 1993-10-07 EP EP93116251A patent/EP0596273B1/fr not_active Expired - Lifetime
- 1993-10-07 ES ES93116251T patent/ES2114991T3/es not_active Expired - Lifetime
- 1993-10-07 DK DK93116251T patent/DK0596273T3/da active
- 1993-10-07 AT AT93116251T patent/ATE165876T1/de active
- 1993-10-07 DE DE59308502T patent/DE59308502D1/de not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3010854A (en) * | 1954-12-31 | 1961-11-28 | Armco Steel Corp | Pickling solution and method |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2114991T3 (es) | 1998-06-16 |
| EP0596273A1 (fr) | 1994-05-11 |
| DK0596273T3 (da) | 1999-02-15 |
| DE59308502D1 (de) | 1998-06-10 |
| ATE165876T1 (de) | 1998-05-15 |
| DE4237021C1 (de) | 1994-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69210622T2 (de) | Zusammensetzung zum stabilisieren anorganischer peroxidlösungen | |
| DE69405876T2 (de) | Zusammensetzung und verfahren zum reinigen und desoxidieren ohne verschmutzung | |
| DE2359021A1 (de) | Beizloesung und verfahren zum beizen von metallen | |
| DE69705993T2 (de) | Beizen von rostfreiem Stahl mit Wasserstoffperoxid enthaltender Lösung | |
| DE2555809A1 (de) | Loesung zum reinigen von oberflaechen aus kupfer und seinen legierungen | |
| DE1161740B (de) | Verfahren zum Beizen von legierten Staehlen | |
| EP0596273B1 (fr) | Produits de décapage de surfaces d'aciers au chromenickel ou d'aciers du chrome et leur utilisation | |
| DE1290410B (de) | Waessrige, saure Fluorid-Ionen und einen anorganischen Inhibitor enthaltende Loesung, die praktisch frei von Chlorid-Ionen ist, und Verfahren zum Reinigen von Aluminium und Aluminiumlegierungen | |
| DE69304516T2 (de) | Verfahren und zusammensetzung zur reinigung von aluminium- und aluminiumlegierungsoberflächen | |
| EP2352860B1 (fr) | Procédé destiné au traitement de surfaces en acier inoxydable | |
| DE69404711T2 (de) | Verwendung einer sauren, wässrigen Reinigungslösung für Aluminium und Al-Legierungen und Verfahren zum Reinigen | |
| DE2847267A1 (de) | Einstufiges, vorzugsweise mehrstufiges verfahren zum beizen und/oder chemischen glaenzen von kupfer oder kupferlegierungen | |
| DE10160318A1 (de) | Verfahren zum Beizen von martensitischem oder ferritischem Edelstahl | |
| DE3222532C2 (fr) | ||
| DE1220699B (de) | Beizbad fuer rostfreien Stahl | |
| DE9214890U1 (de) | Mittel zum Beizen und/oder Reinigen von Metalloberflächen | |
| DE69219072T2 (de) | Verfahren zum kontinuierlichen Beizen von Stahl-Material in einer Behandlungsstrasse | |
| DE2710459C2 (de) | Verfahren zum elektrolytischen Entzundern eines metallischen Körpers und seine Anwendung auf legierten Stahl | |
| DE10156624B4 (de) | Verfahren und Beizlösung zum Abreinigen von Belägen eines Stahl-Werkstückes | |
| DE19624436A1 (de) | Verfahren zur Oberflächenbehandlung von aus Edelstahl bestehendem Behandlungsgut | |
| EP1100982B1 (fr) | Decapant pour aciers speciaux | |
| DE1621611A1 (de) | Verfahren und Loesung zum Beizen von Kupferlegierungen | |
| DE3801018A1 (de) | Verfahren zum entfernen von zunder und oxyden von metallen, metallegierungen, insbesondere legierten staehlen, hochlegierten staehlen und kohlestaehlen mittels eines eisen(iii)-ionen enthaltenden beizbades | |
| EP1913181A1 (fr) | Procede d'electropolissage | |
| EP0626469A1 (fr) | Procédé de décapage de pièces en matériaux hautement alliés |
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 CH DE DK ES FR GB IT LI LU NL SE |
|
| 17P | Request for examination filed |
Effective date: 19940323 |
|
| 17Q | First examination report despatched |
Effective date: 19940705 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: POLIGRAT - HOLDING GESELLSCHAFT MBH |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: POLIGRAT GMBH |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
| REF | Corresponds to: |
Ref document number: 165876 Country of ref document: AT Date of ref document: 19980515 Kind code of ref document: T |
|
| ITF | It: translation for a ep patent filed | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REF | Corresponds to: |
Ref document number: 59308502 Country of ref document: DE Date of ref document: 19980610 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2114991 Country of ref document: ES Kind code of ref document: T3 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19980623 |
|
| ET | Fr: translation filed | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981007 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981007 Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981007 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981007 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981008 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981008 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981031 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981031 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| 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 | ||
| BERE | Be: lapsed |
Owner name: POLIGRAT G.M.B.H. Effective date: 19981031 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 19990501 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19981007 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| EUG | Se: european patent has lapsed |
Ref document number: 93116251.5 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990630 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19990501 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| 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: 19990803 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19991113 |
|
| 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: 20051007 |