EP3449040A1 - Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel - Google Patents
Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steelInfo
- Publication number
- EP3449040A1 EP3449040A1 EP17721118.2A EP17721118A EP3449040A1 EP 3449040 A1 EP3449040 A1 EP 3449040A1 EP 17721118 A EP17721118 A EP 17721118A EP 3449040 A1 EP3449040 A1 EP 3449040A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pickling
- composition
- formula
- range
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005554 pickling Methods 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 title abstract description 8
- 239000002184 metal Substances 0.000 title abstract description 8
- 229910000831 Steel Inorganic materials 0.000 title abstract description 6
- 239000010959 steel Substances 0.000 title abstract description 6
- 239000000463 material Substances 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- IXAWTPMDMPUGLV-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)but-2-ynoxy]ethanol Chemical compound OCCOCC#CCOCCO IXAWTPMDMPUGLV-UHFFFAOYSA-N 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 235000021110 pickles Nutrition 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000003112 inhibitor Substances 0.000 description 13
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWPNNZKRAQDVPZ-UHFFFAOYSA-N 1,3-bis(2-methylphenyl)thiourea Chemical compound CC1=CC=CC=C1NC(=S)NC1=CC=CC=C1C KWPNNZKRAQDVPZ-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002110 toxicologic effect Effects 0.000 description 2
- 231100000027 toxicology Toxicity 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 150000002363 hafnium compounds Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- UBUHAZKODAUXCP-UHFFFAOYSA-N iron(2+);oxygen(2-);hydrate Chemical class O.[O-2].[Fe+2] UBUHAZKODAUXCP-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 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 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium 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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
-
- 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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- 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
-
- 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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
-
- 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
- C23G1/081—Iron or steel solutions containing H2SO4
-
- 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
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
-
- 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
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
Definitions
- the invention relates to an aqueous composition for reducing pickling during pickling of metallic surfaces containing bare and / or galvanized steel and to a process for pickling a corresponding metallic surface with reduced pickling.
- Atmospheric corrosion or heat treatment e.g., heat generation during forming or welding
- pickling means the dissolution of these oxide layers in mineral acid solutions in order to achieve a metallically clean surface for further processing.
- This essentially serves to remove oxide films of rust - FeO, Fe 2 O 3 , Fe 3 O 4 and iron oxide hydrates - or zinc oxide from the surface, which in turn increases the adhesive strength and uniformity of subsequent coatings, in particular a conversion coating on the surface.
- the object of the invention was therefore to provide a composition for reducing pickling during pickling of metallic surfaces containing bare and / or galvanized steel and a method for pickling a corresponding metallic surface with reduced pickling removal, which or which completely with a subsequent Conversion treatment is compatible and toxicologically less harmful and less harmful to the environment.
- the formation of the conversion coating are not adversely affected as well as a water-wettable surface are available.
- the service life of a corresponding pickling bath should preferably be increased by the reduced pickling removal.
- This object is achieved by a composition according to claim 1, a concentrate according to claim 7, a method according to claim 8 and a use according to claim 15.
- Advantageous embodiments are each described in the dependent claims.
- the aqueous composition according to the invention for reducing pickling during pickling of metallic surfaces containing bare and / or galvanized steel contains a mixture of a compound of the formula I.
- an "aqueous composition” is to be understood to mean one which contains water, for the most part, ie more than 50% by weight, as the solvent / dispersant,
- the aqueous composition is a solution, more preferably about a solution containing only water as a solvent.
- the "galvanized steel” may in the present case be both electrolytically galvanized and hot-dip galvanized steel.
- Compounds of Formula I act as physical corrosion inhibitors adsorbed to the metallic surface by van der Waals forces, forming a monomolecular, homogeneous, densely packed layer thereon. By means of said layer, the metallic surface is physically at least partially shielded from a proton attack and thus the pickling removal of the surface is prevented or at least reduced. It was surprisingly found that the use of certain mixtures of different compounds of the formula I, a significant synergy effect can be achieved with respect to a reduction of pickling.
- the aqueous composition according to the invention is essentially free from ⁇ , ⁇ '-diethylthiourea, N, N'-di (o-tolyl) thiourea, ⁇ , ⁇ '-dibutylthiourea and hexamethylenetetraamine.
- Substantially free means that the abovementioned compounds were not deliberately added to the composition, that is to say they are at most impurities in the starting materials used
- the total content of these compounds in the composition according to the invention is preferably below 5 mg / l, more preferably below 1 mg / l.
- The% by weight mixing ratio of the compound of formula I in which R 1 and R 2 are both H and the compound of formula I wherein R 1 and R 2 are each independently HO- (CH 2 ) W Group with w> 2 is preferably in the range of 0.5: 1 to 2: 1, more preferably in the range of 0.75: 1 to 1, 75: 1 and most preferably in the range 1: 1 to 1, 5: 1 (calculated as 2-butyne-1, 4-diol and 2-butyne-1, 4-diol-bis (2-hydroxyethyl ether)).
- the sum of x and y is 2 to 5. More preferably, the aqueous composition contains a mixture of 2-butyne-1, 4-diol and 2-butyne-1, 4-diol bis (2-hydroxyethylether).
- the mixing ratio based on% by weight is again preferably in the range from 0.5: 1 to 2: 1, more preferably in the range from 0.75: 1 to 1:75: 1 and most preferably in the range 1: 1 to 1, 5: 1.
- the composition additionally contains at least one compound of formula II
- the at least one compound of the formula II is preferably HO-CH 2 -S-CH 2 .
- the aqueous composition according to the invention can be obtained from the concentrate according to the invention by dilution with a suitable solvent and / or dispersion medium, preferably with water, and optionally adjusting the pH.
- the dilution factor when adding the concentrate to the pickling solution in step ii) is preferably in the range from 1:23 to 1: 225.
- the dilution factor when adding the concentrate to the rinse solution in step iii) is preferably in the range from 1: 225 to 1: 2250.
- the surface is formed in successive process steps i) optionally cleaned and / or rinsed,
- iii) is brought into contact with an aqueous rinsing composition, wherein the pickling composition in step ii) and / or the rinsing composition in step iii) at least one composition according to the invention as described above.
- the pickling composition ii) preferably contains at least one compound selected from the group consisting of phosphonates, condensed phosphates and citrate and / or at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, more preferably it contains at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, most preferably it contains sulfuric acid.
- the pH of the rinsing composition in step iii) is preferably strongly acidic, neutral or slightly alkaline, more preferably in the range from 2 to 8.
- the pickling composition in step ii) is a composition according to the invention as described above.
- the total concentration of the mixture of the two compounds of the formula I in the mordant composition is preferably in the range from 31 to 620 mg / l, particularly preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1, 4-diol).
- the use of the mixture of the two compounds of the formula I in the pickling composition has the advantage of particularly effectively reducing pickling.
- the rinsing composition in step iii) is a composition according to the invention as described above.
- the total concentration of the mixture of the two compounds of the formula I in the rinsing composition is preferably in the range from 3 to 62 mg / l, particularly preferably in the range from 3 to 31 mg / l (calculated as 2-butyne-1,4-diol).
- the pickling composition in step ii) and the rinsing composition in step iii) are each a composition according to the invention as described above. In the mixing of the two compounds of the formula I in the pickling composition and in the rinsing composition may be the same or a different mixture.
- the total concentration of the mixture of the two compounds of formula I in the pickling composition is again preferably in the range from 31 to 620 mg / l, more preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1, 4-diol ) and in the rinsing composition preferably in the range of 3 to 62 mg / l, more preferably in the range of 3 to 31 mg / l (calculated as 2-butyne-1, 4-diol).
- metallic surface containing bare and / or galvanized steel to the surface of a metallic component / workpiece, such as a steel pipe, of wires or screws (general cargo).
- the pickled with the inventive method metallic surface is therefore preferably used in the field of parts treatment.
- the pickled and rinsed metallic surface is preferably first conversion treated.
- For the conversion treatment is preferably a acid aqueous composition containing zinc phosphate, manganese phosphate and optionally nickel ions (so-called zinc phosphating).
- an acidic aqueous composition which comprises a titanium, zirconium and / or hafnium compound and optionally copper ions and / or a compound which liberates copper ions, if appropriate a polymer and / or copolymer and, if appropriate, one Organoalkoxysilane and / or a hydrolysis and / or a condensation product thereof.
- a base coat which is preferably a cathodic electrodeposition paint (KTL), more preferably a (meth) acrylate- or epoxy-based KTL, is applied, and then a top coat is applied.
- KTL cathodic electrodeposition paint
- a lubricant containing salts, polymers and / or soaps is applied to the pickled and rinsed metallic surface.
- the present invention is to be illustrated by the following - not to be limited - embodiments.
- Aqueous pickling solutions A to E were prepared, each containing 20% by weight of H 2 SO 4 , 50 g / L of Fe 2+ and optionally one or two pickling inhibitors.
- Test panels of CRS cold rolled steel were each weighed before treatment with one of the pickling solutions.
- pickling inhibitors of pickling solutions B and C thus each had an excellent inhibition of 96%.
- the inhibition values of the individual inhibitors but-2-yn-1,4-diol (pickling solution D) and 2-butyne-1,4-diol bis (2-hydroxyethyl ether) (pickling solution E) remained significant at 85% and 92%, respectively behind it.
- the inhibition value of the mixture according to the invention of the latter two pickling inhibitors was surprisingly high at 97% and even exceeded that of the abovementioned pickling inhibitors to be avoided.
- the sheets were subsequently zinc-phosphated.
- the pickling solutions B and F were added to the phosphating bath in increasing amounts.
- the appearance of the metal sheets was evaluated.
- the layer weights in g / m 2 calculated from P2O 5 were determined by means of RFA.
- the mixture according to the invention not only reduces the pickling rate, but also leads to no disruption of film formation in a subsequent phosphating step, for example as a result of the carryover of the pickling solution.
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL17721118T PL3449040T3 (en) | 2016-04-29 | 2017-04-28 | Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel |
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DE102016207429 | 2016-04-29 | ||
PCT/EP2017/060227 WO2017186929A1 (en) | 2016-04-29 | 2017-04-28 | Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel |
Publications (2)
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EP3449040A1 true EP3449040A1 (en) | 2019-03-06 |
EP3449040B1 EP3449040B1 (en) | 2020-03-18 |
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EP17721118.2A Active EP3449040B1 (en) | 2016-04-29 | 2017-04-28 | Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel |
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US (1) | US11124884B2 (en) |
EP (1) | EP3449040B1 (en) |
JP (1) | JP6968825B2 (en) |
KR (1) | KR102369545B1 (en) |
CN (1) | CN109072454B (en) |
DE (1) | DE102017207232A1 (en) |
ES (1) | ES2795655T3 (en) |
MX (1) | MX2018013233A (en) |
PL (1) | PL3449040T3 (en) |
RU (1) | RU2747720C2 (en) |
WO (1) | WO2017186929A1 (en) |
ZA (1) | ZA201807922B (en) |
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WO2018102724A1 (en) * | 2016-12-02 | 2018-06-07 | Ecolab Usa Inc. | Thiol-formyl hemiacetal corrosion inhibitors |
DK3662034T3 (en) | 2017-08-03 | 2023-05-15 | Championx Usa Inc | THIOL ADDUCTORS FOR CORROSION INHIBIT |
MX2020006184A (en) | 2017-12-12 | 2020-09-03 | Chemetall Gmbh | Boric acid-free composition for removing deposits containing cryolite. |
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US3310497A (en) | 1965-02-23 | 1967-03-21 | United States Steel Corp | Embrittlement-free pickling of ferrous metal |
FR1475895A (en) | 1966-02-23 | 1967-04-07 | Framalite Soc | New synergistic metal corrosion inhibitor |
FR2158664A5 (en) | 1971-10-27 | 1973-06-15 | Nivoxal Procedes | Metal surface treatment baths - additive - for addition to hydrochloric and sulphuric acid based baths |
DE2507059A1 (en) | 1975-02-19 | 1976-09-02 | Basf Ag | Degreasing and pickling iron articles - with acid baths contg. water-soluble aromatic nitro cpd. oxidising agents |
US4302246A (en) * | 1980-01-03 | 1981-11-24 | Enthone, Incorporated | Solution and method for selectively stripping alloys containing nickel with gold, phosphorous or chromium from stainless steel and related nickel base alloys |
US5843373A (en) * | 1997-08-22 | 1998-12-01 | Betzdearborn Inc. | Corrosion inhibitor for alkanolamine units |
JP4241821B2 (en) * | 2003-02-24 | 2009-03-18 | ビーエーエスエフ ソシエタス・ヨーロピア | Carboxylate-containing polymer for metal surface treatment |
CA2539246A1 (en) * | 2003-09-30 | 2005-04-14 | Basf Aktiengesellschaft | Method for pickling metallic surfaces by using alkoxylated alkynols |
DE10345801A1 (en) | 2003-09-30 | 2005-04-14 | Basf Ag | Pickling metal surface, e.g. iron, steel, zinc, brass or aluminum, especially strip, uses acid aqueous composition containing ethoxylated or propoxylated prop-1-yn-3-ol or but-2-yn-1,4-diol as inhibitor |
KR20050044085A (en) | 2003-11-07 | 2005-05-12 | 삼성전자주식회사 | Aqueous cleaning solution for integrated circuit device and cleaning method using the cleaning solution |
AU2007217257B2 (en) * | 2006-02-23 | 2013-08-01 | Henkel Ag & Co. Kgaa | Acid inhibitor compositions for metal cleaning and/or pickling |
US8278258B2 (en) * | 2007-02-01 | 2012-10-02 | Henkel Ag & Co. Kgaa | Acid inhibitor compositions for metal cleaning and/or pickling |
WO2010055160A2 (en) | 2008-11-17 | 2010-05-20 | Basf Se | Use of thiodiglycol ethoxylate as a corrosion inhibitor |
CN102011129A (en) * | 2010-12-14 | 2011-04-13 | 南通飞拓生物科技有限公司 | Corrosion inhibitor |
CN102330099B (en) * | 2011-09-09 | 2013-11-06 | 北京星航机电设备厂 | Stainless steel pickling inhibitor |
RU2539129C1 (en) * | 2013-08-19 | 2015-01-10 | Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) | Inhibitor of acid metal corrosion |
MX2016014200A (en) * | 2014-04-30 | 2017-05-03 | Rio Verwaltungs Ag | Treatment device and treatment method for pickling and phosphating metal parts. |
MX2018013229A (en) | 2016-04-29 | 2019-02-13 | Chemetall Gmbh | Method for anti-corrosion treatment of a metal surface with reduced pickling material. |
WO2017202891A1 (en) | 2016-05-25 | 2017-11-30 | Chemetall Gmbh | Process for corrosion-protecting phosphatization of a metallic surface with reduced pickling erosion |
-
2017
- 2017-04-28 JP JP2018556914A patent/JP6968825B2/en active Active
- 2017-04-28 ES ES17721118T patent/ES2795655T3/en active Active
- 2017-04-28 CN CN201780024275.0A patent/CN109072454B/en active Active
- 2017-04-28 PL PL17721118T patent/PL3449040T3/en unknown
- 2017-04-28 DE DE102017207232.6A patent/DE102017207232A1/en not_active Withdrawn
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- 2017-04-28 KR KR1020187030705A patent/KR102369545B1/en active IP Right Grant
- 2017-04-28 RU RU2018140856A patent/RU2747720C2/en active
- 2017-04-28 US US16/097,134 patent/US11124884B2/en active Active
- 2017-04-28 WO PCT/EP2017/060227 patent/WO2017186929A1/en active Application Filing
- 2017-04-28 EP EP17721118.2A patent/EP3449040B1/en active Active
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Also Published As
Publication number | Publication date |
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KR102369545B1 (en) | 2022-03-03 |
RU2018140856A (en) | 2020-05-29 |
ES2795655T3 (en) | 2020-11-24 |
WO2017186929A1 (en) | 2017-11-02 |
BR112018071497A2 (en) | 2019-02-19 |
US20190112717A1 (en) | 2019-04-18 |
US11124884B2 (en) | 2021-09-21 |
ZA201807922B (en) | 2020-02-26 |
PL3449040T3 (en) | 2020-08-24 |
DE102017207232A1 (en) | 2017-11-02 |
KR20190003514A (en) | 2019-01-09 |
RU2018140856A3 (en) | 2020-06-25 |
EP3449040B1 (en) | 2020-03-18 |
JP6968825B2 (en) | 2021-11-17 |
MX2018013233A (en) | 2019-02-13 |
JP2019515133A (en) | 2019-06-06 |
CN109072454B (en) | 2021-03-05 |
CN109072454A (en) | 2018-12-21 |
RU2747720C2 (en) | 2021-05-13 |
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