EP2215285A1 - Phosphatation au zirconium de pièces métalliques, en particulier en fer - Google Patents
Phosphatation au zirconium de pièces métalliques, en particulier en ferInfo
- Publication number
- EP2215285A1 EP2215285A1 EP08853163A EP08853163A EP2215285A1 EP 2215285 A1 EP2215285 A1 EP 2215285A1 EP 08853163 A EP08853163 A EP 08853163A EP 08853163 A EP08853163 A EP 08853163A EP 2215285 A1 EP2215285 A1 EP 2215285A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ppm
- treatment solution
- zirconium
- hollow body
- pretreatment
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title abstract description 21
- 239000002184 metal Substances 0.000 title abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 83
- 238000011282 treatment Methods 0.000 claims abstract description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000011253 protective coating Substances 0.000 claims abstract description 3
- 238000004070 electrodeposition Methods 0.000 claims description 29
- 239000003973 paint Substances 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001273 Polyhydroxy acid Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 32
- 239000011248 coating agent Substances 0.000 abstract description 26
- 239000004922 lacquer Substances 0.000 abstract description 4
- 238000010422 painting Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 45
- 230000008569 process Effects 0.000 description 37
- 229910019142 PO4 Inorganic materials 0.000 description 20
- 239000010452 phosphate Substances 0.000 description 20
- 238000002161 passivation Methods 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- -1 phosphate anions Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 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 4
- 238000001994 activation Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 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 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 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
- 150000003755 zirconium compounds Chemical class 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
- C23C22/361—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 fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4935—Heat exchanger or boiler making
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
Definitions
- the present invention relates to a process for the corrosion-protective pretreatment of metallic components which at least partially comprise metallic iron surfaces, with a chromium-free aqueous treatment solution containing fluorocomplexes of zirconium and / or titanium and phosphate ions in a specific ratio range to each other, and a metallic component, which has been pretreated accordingly, and its use for the application of further anti-corrosive coatings and / or paint systems.
- the method is particularly suitable as a pretreatment for an electrodeposition coating of metallic components, which are in the form of non-closed hollow bodies.
- the present invention therefore also relates to a process for coating a non-closed metallic hollow body, which comprises both the pretreatment with the chromium-free aqueous treatment solution and a subsequent electrodeposition coating, and a metallic hollow body which is coated according to the inventive method, and its use for the production of radiators.
- the passivation of metallic materials is ensured primarily by the zinc or iron phosphating.
- zinc or iron phosphating mostly crystalline inorganic coatings are produced on the metallic base material, which have a layer thickness of several micrometers and, due to their surface topography, have excellent adhesion to organic cover layers, especially to coating systems applied in the electrocoating process.
- non-film-forming iron phosphating the conversion becomes the metal surface is typically made in a phosphoric acid medium also in the presence of accelerators and wetting agents at elevated bath temperature.
- Such iron phosphate layers rarely have layer weights of more than 1 g / m 2 and, in contrast to phosphations with high layer weights, are amorphous.
- the classical phosphating is a multi-step process consisting of a cleaning step to degrease the component, an activation process and ultimately the actual phosphating, wherein for decoupling the process baths in continuous operation rinsing steps are installed.
- a rinsing process is obligatory, at least after the cleaning step, so that the phosphating is composed of at least four individual processes which have to be monitored and controlled in terms of process technology in individual baths.
- Additional alternative methods of standard phosphating which provide coating weights of significantly more than 1 g / m 2 , are, in addition to the non-layering iron phosphating, conversion treatments of the metallic surfaces to form purely amorphous, inorganic passive layers with much lower coating weights of the order of magnitude less as 200 mg / m 2 .
- any pretreatment processes that produce such "non-film-forming" (non-crystalline) phosphating and / or metal surface conversion have the advantage of rendering surface activation unnecessary and can thus be saved in the process chain of pretreatment.
- Another advantage over the layer-forming zinc phosphating is the reduction of phosphate sludge in the phosphating baths.
- US Pat. No. 5,356,490 and WO 04/063414 teach phosphate-free and chromium-free aqueous treatment solutions containing zirconium and / or titanium compounds which are deposited on the metallic component in the acidic medium as a so-called passivating conversion layer due to the pickling attack of the treated metallic surfaces.
- Both documents teach that dispersed water-insoluble inorganic compounds must additionally be present in order to achieve the desired effect with regard to corrosion protection and paint adhesion
- WO 04/063414 explicitly requiring the presence of acid-stable, nanodispersed compounds based on silica and, in contrast to US Pat 5,356,490 works without the addition of organic polymers.
- DE 1933013 also discloses phosphate-free treatment baths having a pH above 3.5, in addition to complex fluorides of boron, titanium or zirconium in amounts of 0.1 to 15 g / l, based on the metals, in addition 0.5 to 30 g / l oxidizing agent, in particular sodium m-nitrobenzenesulfonate included.
- the function of the oxidizing agent sodium m-nitrobenzenesulfonate is to vary the treatment duration of the metal surfaces to a particularly large extent.
- WO 03/002781 discloses pretreatment solutions comprising not only phosphoric acid but also fluorocomplexes of zirconium and / or titanium and a homo- or copolymer of vinylpyrrolidone.
- Such a pretreatment solution provides low mass mixed amorphous mixed organic / inorganic passivations which may be provided with an electrodeposition paint.
- DE 2715292 discloses treatment baths for chromium-free pretreatment of aluminum cans containing at least 10 ppm of titanium and / or zirconium, between 10 and 1000 ppm of phosphate and a sufficient amount of fluoride to form complex fluorides of the existing titanium and / or zirconium, but at least 13 ppm and pH values between 1, 5 and 4.
- the object of the present invention is therefore to provide a conversion treatment of metallic components consisting at least partially of iron, which provides at least comparable or improved results in terms of corrosion protection and electrodeposition paint consumption over the non-layer-forming treatment methods known in the prior art, but without the to have to resort to complex and energy-intensive process steps of the layer-forming phosphating.
- the alternative process is intended to provide a corrosion-protected metallic process in as few process steps as possible that are easy to control Provide surface, especially iron surface, and on the other hand, as possible to save resources while avoiding difficult to work up residues, such as phosphate sludge, be feasible.
- such an alternative method must ensure the subsequent electrocoating of the treated metallic component, preferably in the form of a non-closed hollow body, with optimum lacquer coverage always aiming at the lowest possible paint consumption.
- This object is first achieved by a method for corrosion-protective pretreatment, wherein the component to be treated, which at least partially has metallic surfaces of iron, with a chromium-free aqueous treatment solution containing (i) not less than 50 ppm and not more than 1000 ppm zirconium and / or titanium in the form of their fluoro complexes, as well
- the metallic component preferably consists entirely of iron and / or an iron alloy with a content of more than 50 At. -% of iron or of surfaces whose iron content is greater than 50 at.%.
- the treatment solution does not require any additions of chromium compounds and is therefore chromium-free for ecological reasons and to ensure a high level of occupational safety.
- ions of chromium in a low concentration enter the pretreatment solution from the container material or from the surfaces to be treated, for example steel alloys.
- concentration of chromium in the ready-to-use processing solution is not higher than about 10 ppm, preferably not higher than 1 ppm.
- the pH of the treatment solution can be arbitrarily adjusted by adding dilute nitric acid or ammoniacal solution in the specified range.
- the pH of the treatment solution is particularly preferably below 5.5, in particular below 5.0.
- the performance of the pretreatment with regard to corrosion resistance of the treated components and the throw-over behavior in a subsequent electrodeposition coating can be adjusted.
- excessively high ratios of zirconium and / or titanium to the phosphate present in the treatment solution as well as excessively low relative zirconium and / or titanium contents have a significantly negative influence on the picking behavior.
- An optimum result, that is to say maximum permeation in the paint deposition, is achieved in particular if the molar ratio of zirconium and / or titanium to phosphate ions is not set to be smaller than 1: 1.
- zirconium compounds in the different embodiments of the present invention gives technically better results than the use of titanium compounds and is therefore preferred.
- complex fluoro acids or their salts can be used.
- those treatment solutions which are preferred as component (i) are at least 150 ppm, preferably at least 200 ppm, but not more than 350 ppm, preferably not more than 300 ppm zirconium in the form of a fluorocomplex.
- the phosphate content of the treatment solution according to the invention is extremely low in comparison with zinc or iron phosphating baths described in the prior art.
- a low concentration of phosphate ions of at least 10 ppm in combination with the fluorocomplexes of zirconium and or titanium leads to the formation of a thin amorphous zirconium and / or titanium phosphate layer and thus to the desired passivation of the metal surface, in particular the iron surface.
- a homogeneous passivation takes place already at phosphate contents of preferably 30 ppm, more preferably at least 60 ppm.
- the phosphate content should not exceed 1000 ppm and preferably not more than 180 ppm, more preferably not more than 120 ppm phosphate ions.
- accelerators known from zinc and iron phosphating promote the formation of a homogeneous passivation.
- Such accelerators are oxidizing agents which perform the task of a "hydrogen scavenger" in phosphating, by directly oxidizing and thereby reducing the hydrogen produced by the acid attack on the metallic surface
- the accelerators in the non-film-forming iron phosphating in which layer thicknesses of not significantly more than one micrometer are produced Homogeneous formation of an amorphous, only a few nanometers passive layer based on zirconium and / or titanium phosphate support, however, the activity of the accelerators in the treatment bath is wet lower than is the case, for example, in zinc phosphating, so that typical oxidizing agents should be used at levels not greater than 1000 ppm, but at least 10 ppm must be present in the treating solution to promote zirconium- and / or titanium-based passivation of the ferrous metal surface.
- Typical representatives of the oxidizing agents are chlorate ions, nitrite ions, nitroguanidine, N-methylmorpholine-N-oxide, m-nitrobenzoate-ions, p-nitrophenol, m-nitrobenzenesulfonate ions, hydrogen peroxide in free or bound form, hydroxylamine in free or bound form, reducing Sugar.
- m-nitrobenzenesulfonate as accelerator at levels of not less than 20 ppm, preferably not less than 50 ppm and not more than 500 ppm, preferably not more than 300 ppm, significantly improved passivation properties of the treatment solution are achieved.
- a further improvement of the passive layer properties and the adhesion to subsequently applied lacquer layers results when adding particulate inorganic, water-insoluble compounds of the elements silicon, aluminum, zinc, titanium, zirconium, iron, calcium and / or magnesium, the content of these compounds in the treatment solution based on the element is at least 10 ppm, but should not exceed 200 ppm in order not to destabilize the treatment solution by agglomeration and sedimentation of the particulate components.
- the oxidic compounds of said elements are used in nanoparticulate form.
- the German patent application DE 100 05 113 is based on the finding that homo- or copolymers of vinylpyrrolidone have an excellent corrosion protection effect.
- the chromium-free treatment solution may therefore additionally preferably contain at least 50 ppm, more preferably 200 ppm, but not more than 1000 ppm of homopolymers or copolymers of vinylpyrrolidone in the process according to the invention.
- a further feature of the present invention is that the process preferably without the addition of other organic polymers as such, which are polymers based on homopolymers or copolymers of vinylpyrrolidone, is feasible.
- organic polymers as such, which are polymers based on homopolymers or copolymers of vinylpyrrolidone
- polymers having hydroxyl and / or carboxyl functionalities are often added in substantial amounts (> 1 g / l) to the passivation baths in order to act as binders in the inorganic passive layer to act as further binders to subsequently applied organic coatings.
- the process of the present invention should be adjusted to phosphate ion ratios with respect to molar ratios of zirconium and / or titanium to reduce the rinse time and rinse water level be that of a polymer addition can be waived entirely. Therefore, the present invention also includes those methods in which the molar ratio of zirconium and / or titanium to phosphate ions is not less than 1: 1 and the amount of organic polymers in the treating solution is not more than 1 ppm.
- the inventive method requires no further inorganic additives selected from oxo anions of vanadium, tungsten and / or molybdenum, in order to produce a sufficient passivation of the metal surface, in particular iron surface.
- the treatment solution explicitly contains no oxo anions of the type described above, so that the content of these compounds is by definition in particular not greater than 1 ppm.
- these oxoanions in particular vanadates and molybdates
- the proportion of these compounds in the treatment solution of the process according to the invention relative to the respective element is preferably less than 50 ppm, more preferably less than 10 ppm.
- the treatment solution may additionally contain chelating substances.
- chelating substances in particular those based on ⁇ -hydroxycarboxylic acids, stabilizes the pickling rate in the treatment bath for a longer service life of a bath, so that largely independent of the content of the metal ions, the by pickling the metal surface into the Bad, constant coating conditions of the zirconium and / or titanium-based phosphate layer result.
- the sludge formation consisting of sparingly soluble metal hydroxides can be significantly minimized.
- the chelating substances are added as an additive to the treatment solution in the process according to the invention selected from ⁇ -hydroxycarboxylic acids, more preferably selected from polyhydroxy acids having not more than 8 carbon atoms, in particular gluconic acid is preferred.
- the content of chelating substances in the treatment solution of the process according to the invention is preferably at least 0.01% by weight, more preferably at least 0.05% by weight, but preferably not more than 2% by weight, more preferably not more than 1 wt .-%.
- the metallic component to be treated in the method according to the invention is optionally previously removed in a cleaning step from superficial impurities, in particular from lubricating and / or corrosion protection oils freed. If such a cleaning is omitted, it is not possible to achieve a passivation homogeneously formed over the entire metal surface of the component in the method according to the invention.
- the acidic treatment solution of the process according to the invention may additionally comprise at least one surface-active substance, so that the effective cleaning of the metal surfaces of the component and their passivation are associated with one another.
- the use of surface-active substances in passivating pretreatment solutions is not self-evident and thus surprising in the process according to the invention.
- So 1933013 (Bonderite NT ®) takes place for example in the presence of nonionic surfactants in phosphate-free treatment baths according to DE insufficient passivation of the metal surface.
- Suitable surface-active substances all common surfactants, preferably nonionic surfactants can be used in principle, which are stable in the treating solution of the present process and a low critical micelle concentration of less than 10 -3 mol / l, preferably at below 10 "4 mol / l.
- the passivating pretreatment process according to the invention is preferably carried out at bath temperatures of the treatment solution of not more than 40 ° C. If the pretreatment solution additionally contains surface-active substances, then the bath temperature for adequate cleaning of the metal surfaces of the component to be treated is preferably at least 30 ° C., where higher bath temperatures than 80 ° C. are not required and have a negative effect on the energy efficiency of the method.
- the metal surfaces may be brought into contact with the pretreatment solution by either dipping or spraying.
- the present invention also includes a method of anti-corrosive coating of non-closed metallic Hollow bodies which have at least partially metallic surfaces of iron, wherein the previously described inventive method for anticorrosive pretreatment followed by an electrodeposition coating with or without intermediate rinsing step.
- amorphous and extremely thin zirconium and / or titanium-based phosphate passivation after electrocoating shows a compared to electrocoated crystalline phosphate coatings acceptable corrosion resistance and paint adhesion.
- such non-closed metallic hollow bodies are to be at least partially coated with iron surfaces in which the ratio of the inner surface area of the non-closed hollow body to the opening area of the same is not less than 5, that is, for example, at least cube-shaped.
- the Umgriff so the deposition of the dip paint on the opposite sides of the counter electrode electrode or on the inner regions of the metallic hollow body, which are almost field-free due to their Faraday shielding at the beginning of the deposition and therefore only accessible via the resistance structure of the depositing paint layer for film formation is determined decisively by the passivating pretreatment according to the invention and can therefore also be used as a characterizing feature of the pretreatment according to the invention or of the coating according to the invention.
- the process-specific limitation of the layer thickness of the electro-dip is decisive for the encirclement of the paint, as with the same amount of charge, but lesser limited or maximum coating thickness, inevitably a better throwing takes place.
- a specific layer thickness limit as the ratio of the layer thickness of the electrodeposition paint on the outer surface of a coated according to the invention hollow body to the thickness of the electrodeposition paint after identical, but only electrocoating without prior pre-treatment on the identical outer surface of an identical untreated, but be specified purified and degreased hollow body. This should not be greater than 0.95, preferably not greater than 0.9, and more preferably not greater than 0.8 according to the present invention.
- the method according to the invention for coating a metallic hollow body can be carried out in such a way that a rinsing step takes place between the method steps of the pretreatment according to the invention and the electrocoating step, preferably with deionized water or city water.
- no drying of the metallic hollow body takes place after the pretreatment according to the invention and before the electrocoating process step.
- the present invention likewise relates to the metallic components and non-closed metallic hollow bodies treated directly with the method according to the invention for the pretreatment and coating, wherein the metallic components and hollow bodies to be treated at least partially have metallic iron surfaces.
- the present invention encompasses the use of a metallic component whose entire surface, which consists at least partly of metallic iron surfaces, has been pretreated with the chromium-free aqueous treatment solution in accordance with the method according to the invention for the application of further corrosion-protective coatings and / or organic coating systems.
- the present invention comprises the use of a non-closed metallic hollow body whose entire surface, which consists at least partially of metallic iron surfaces, according to the inventive method first pretreated with the chromium-free aqueous treatment solution and then electrocoated with or without intervening rinsing step, for the production of radiators.
- Embodiments of the invention and comparative examples for the pretreatment of steel sheets (CRS: CoId Rolled Steel) including their subsequent electrodeposition coating are mentioned below.
- CRS sheets are treated by immersion for 5 min at 50 0 C in an aqueous solution composed of 3 wt .-% Ridoline 1562 ® and 0.3 wt .-% Ridosol 1270 ® while stirring the cleaning solution.
- CRS sheets are first cleaned in the immersion process according to the comparative example "alkaline cleaning", after which the cleaned sheet is rinsed for 1 min under running demineralised water (k ⁇ 1 ⁇ Scm -1 ).
- Treatment with Bonderite NT-1 ® (Messrs. Henkel KGaA) a zirconium-containing, but phosphate-free aqueous solution is then carried out by immersion for 1 min at 20 0 C.
- the thus pretreated sheet is then rinsed for 1 min under running demineralised water (k ⁇ 1 ⁇ Scm -1 ).
- CRS sheets are first cleaned in the immersion process according to the comparative example "alkaline cleaning", after which the cleaned sheet is rinsed for 1 min under running demineralised water (k ⁇ 1 ⁇ Scm -1 ).
- the treatment with the commercial product Granodine 958 ® (Messrs. Henkel KGaA) according to the instructions Subsequently, the dipping method. This treatment includes an activation step before the actual phosphating.
- the thus pretreated sheet is then rinsed for 1 min under running deionized water (K ⁇ 1 ⁇ Scm -1 ).
- m-NBS m-nitrobenzenesulfonate
- the average coating thickness is determined by means of the Coating Thickness Gauge PosiTector 6000 (DeFelsko Ltd., Canada) by multiple measurements at different points on the anode-facing side of the sheet.
- the layer thickness of the zinc phosphate layer is first determined by multiple measurement before the electrodeposition coating and subtracted from the determined layer thickness after painting.
- the pretreatment according to the invention has the lowest layer thickness in comparison with the "non-layer-forming" pretreatments with identical electrodeposition coating time, with only the layer-forming phosphated CRS sheet having an even lower paint layer thickness after the electrodeposition coating.
- the undercounter values are comparable to and even better than those found in corrosive infiltration after iron phosphating after 504 hours, which are typically 1.5 mm, and insignificantly larger than after pretreatment with Bonderite NT -1 ® , provides the submarine values of 0.9 mm.
- the whipping behavior is also optimal for CRS sheets which have been pretreated with compositions having the corresponding molar ratios according to the invention (FIG. 2).
- the wraparound is measured and averaged at different points on the side facing away from the anode side of the sheet at different points.
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- 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)
- Chemical Treatment Of Metals (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007057185A DE102007057185A1 (de) | 2007-11-26 | 2007-11-26 | Zirconiumphosphatierung von metallischen Bauteilen, insbesondere Eisen |
PCT/EP2008/066144 WO2009068523A1 (fr) | 2007-11-26 | 2008-11-25 | Phosphatation au zirconium de pièces métalliques, en particulier en fer |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2215285A1 true EP2215285A1 (fr) | 2010-08-11 |
EP2215285B1 EP2215285B1 (fr) | 2016-05-25 |
Family
ID=40282342
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08853163.7A Active EP2215285B1 (fr) | 2007-11-26 | 2008-11-25 | Phosphatation au zirconium de pièces métalliques, en particulier en fer |
Country Status (7)
Country | Link |
---|---|
US (1) | US8663443B2 (fr) |
EP (1) | EP2215285B1 (fr) |
JP (1) | JP2011504550A (fr) |
KR (1) | KR20100102619A (fr) |
DE (1) | DE102007057185A1 (fr) |
ES (1) | ES2584937T3 (fr) |
WO (1) | WO2009068523A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016206417A1 (de) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | Fördergestellbehandlung zur unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung |
WO2017178619A1 (fr) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | Inhibition du transport de phosphates lié au dépôt dans une suite d'opérations jusqu'au laquage par immersion |
EP3569743A1 (fr) | 2018-05-16 | 2019-11-20 | Henkel AG & Co. KGaA | Nettoyage de charriot dans un cycle d'opération de laquage par électro-immersion |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1397902B1 (it) * | 2010-01-26 | 2013-02-04 | Np Coil Dexter Ind Srl | Processi di pretrattamento alla verniciatura, a basso impatto ambientale, alternativi ai trattamenti tradizionali di fosfatazione. |
US9528187B2 (en) | 2010-09-15 | 2016-12-27 | Jfe Steel Corporation | Steel sheet for containers and manufacturing method for same |
US20120094130A1 (en) * | 2010-10-15 | 2012-04-19 | Universidade Estadual De Campinas | Coating Compositions With Anticorrosion Properties |
KR101263086B1 (ko) * | 2010-12-28 | 2013-05-09 | 주식회사 포스코 | 판상형 지르코늄포스페이트 및 그의 제조 방법 |
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DE1933013C3 (de) | 1969-06-28 | 1978-09-21 | Gerhard Collardin Gmbh, 5000 Koeln | Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels komplexe Fluoride enthaltender Lösungen |
US4017335A (en) * | 1975-10-30 | 1977-04-12 | Economics Laboratory, Inc. | Liquid phosphatizing composition and use thereof |
CA1098253A (fr) | 1976-04-05 | 1981-03-31 | Timm L. Kelly | Revetement de protection comportant du zirconium et du titane pour surfaces en aluminium |
JPS5983775A (ja) * | 1982-11-02 | 1984-05-15 | Nippon Paint Co Ltd | 金属表面の化成処理方法 |
US5143562A (en) * | 1991-11-01 | 1992-09-01 | Henkel Corporation | Broadly applicable phosphate conversion coating composition and process |
US5356490A (en) | 1992-04-01 | 1994-10-18 | Henkel Corporation | Composition and process for treating metal |
DE19933189A1 (de) * | 1999-07-15 | 2001-01-18 | Henkel Kgaa | Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen |
US6758916B1 (en) * | 1999-10-29 | 2004-07-06 | Henkel Corporation | Composition and process for treating metals |
DE10005113A1 (de) | 2000-02-07 | 2001-08-09 | Henkel Kgaa | Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen |
DE10131723A1 (de) | 2001-06-30 | 2003-01-16 | Henkel Kgaa | Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen |
US6869513B2 (en) * | 2001-11-08 | 2005-03-22 | Ppg Industries Ohio, Inc. | Photodegradation-resistant electrodepositable coating compositions with improved throw power and processes related thereto |
US6805756B2 (en) * | 2002-05-22 | 2004-10-19 | Ppg Industries Ohio, Inc. | Universal aqueous coating compositions for pretreating metal surfaces |
US7063735B2 (en) * | 2003-01-10 | 2006-06-20 | Henkel Kommanditgesellschaft Auf Aktien | Coating composition |
EP1592824B1 (fr) | 2003-01-10 | 2017-03-08 | Henkel AG & Co. KGaA | Composition de revetement |
DE102005059314B4 (de) * | 2005-12-09 | 2018-11-22 | Henkel Ag & Co. Kgaa | Saure, chromfreie wässrige Lösung, deren Konzentrat, und ein Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen |
US7815751B2 (en) | 2005-09-28 | 2010-10-19 | Coral Chemical Company | Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings |
US8097093B2 (en) * | 2007-09-28 | 2012-01-17 | Ppg Industries Ohio, Inc | Methods for treating a ferrous metal substrate |
-
2007
- 2007-11-26 DE DE102007057185A patent/DE102007057185A1/de not_active Ceased
-
2008
- 2008-11-25 JP JP2010535354A patent/JP2011504550A/ja active Pending
- 2008-11-25 EP EP08853163.7A patent/EP2215285B1/fr active Active
- 2008-11-25 KR KR1020107013990A patent/KR20100102619A/ko not_active Application Discontinuation
- 2008-11-25 WO PCT/EP2008/066144 patent/WO2009068523A1/fr active Application Filing
- 2008-11-25 ES ES08853163.7T patent/ES2584937T3/es active Active
-
2010
- 2010-05-21 US US12/785,120 patent/US8663443B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO2009068523A1 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016206417A1 (de) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | Fördergestellbehandlung zur unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung |
WO2017178619A1 (fr) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | Inhibition du transport de phosphates lié au dépôt dans une suite d'opérations jusqu'au laquage par immersion |
DE102016206418A1 (de) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | Unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung |
US11118271B2 (en) | 2016-04-15 | 2021-09-14 | Henkel Ag & Co. Kgaa | Conveyor frame treatment for suppressing phosphate dragging resulting from the plant design in a dip coating process sequence |
EP3569743A1 (fr) | 2018-05-16 | 2019-11-20 | Henkel AG & Co. KGaA | Nettoyage de charriot dans un cycle d'opération de laquage par électro-immersion |
WO2019219395A1 (fr) | 2018-05-16 | 2019-11-21 | Henkel Ag & Co. Kgaa | Nettoyage de châssis de transport dans une succession de processus de peinture électrophorétique par immersion |
Also Published As
Publication number | Publication date |
---|---|
US8663443B2 (en) | 2014-03-04 |
EP2215285B1 (fr) | 2016-05-25 |
JP2011504550A (ja) | 2011-02-10 |
WO2009068523A1 (fr) | 2009-06-04 |
KR20100102619A (ko) | 2010-09-24 |
DE102007057185A1 (de) | 2009-05-28 |
US20100293788A1 (en) | 2010-11-25 |
ES2584937T3 (es) | 2016-09-30 |
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