EP0454211A1 - Procédé pour appliquer des couches de phosphates sur des surfaces métalliques - Google Patents

Procédé pour appliquer des couches de phosphates sur des surfaces métalliques Download PDF

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Publication number: EP0454211A1
Authority: EP; European Patent Office
Prior art keywords: activating; phosphate; activating agent; copper; amounts
Prior art date: 1990-04-21
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

Application number

EP91200844A

Other languages

German (de)

English (en)

Other versions

EP0454211B1 (fr

Inventor

Rüdiger Rein

Dieter Dr. Jentsch

Klaus-Werner Dr. Wittel

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

GEA Group AG

Continentale Parker SA

Original Assignee

Metallgesellschaft AG

Continentale Parker SA

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1990-04-21

Filing date

1991-04-11

Publication date

1991-10-30

1991-04-11 Application filed by Metallgesellschaft AG, Continentale Parker SA filed Critical Metallgesellschaft AG

1991-10-30 Publication of EP0454211A1 publication Critical patent/EP0454211A1/fr

1994-06-22 Application granted granted Critical

1994-06-22 Publication of EP0454211B1 publication Critical patent/EP0454211B1/fr

2011-04-11 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

229910019142 PO4 Inorganic materials 0.000 title claims abstract description 24
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 22
239000010452 phosphate Substances 0.000 title claims abstract description 21
229910052751 metal Inorganic materials 0.000 title claims abstract description 13
239000002184 metal Substances 0.000 title claims abstract description 13
238000000034 method Methods 0.000 title description 8
230000008569 process Effects 0.000 title description 5
238000000576 coating method Methods 0.000 title description 3
230000003213 activating effect Effects 0.000 claims abstract description 65
239000003795 chemical substances by application Substances 0.000 claims abstract description 50
230000004913 activation Effects 0.000 claims abstract description 28
239000010936 titanium Substances 0.000 claims abstract description 18
239000004094 surface-active agent Substances 0.000 claims abstract description 15
239000010949 copper Substances 0.000 claims abstract description 12
239000011701 zinc Substances 0.000 claims abstract description 11
239000008139 complexing agent Substances 0.000 claims abstract description 10
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
229910052725 zinc Inorganic materials 0.000 claims abstract description 9
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
229920000620 organic polymer Polymers 0.000 claims abstract description 8
229910000831 Steel Inorganic materials 0.000 claims abstract description 7
239000010959 steel Substances 0.000 claims abstract description 7
239000002562 thickening agent Substances 0.000 claims abstract description 7
239000005749 Copper compound Substances 0.000 claims abstract description 6
BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 6
150000001880 copper compounds Chemical class 0.000 claims abstract description 6
229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
229910052742 iron Inorganic materials 0.000 claims abstract description 4
229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 3
239000008397 galvanized steel Substances 0.000 claims abstract description 3
239000003513 alkali Substances 0.000 claims abstract 2
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
229910052719 titanium Inorganic materials 0.000 claims description 10
239000012141 concentrate Substances 0.000 claims description 8
239000007788 liquid Substances 0.000 claims description 7
239000007787 solid Substances 0.000 claims description 7
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
238000002360 preparation method Methods 0.000 claims description 6
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 claims description 5
RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 4
229910000851 Alloy steel Inorganic materials 0.000 claims description 3
229910000680 Aluminized steel Inorganic materials 0.000 claims description 3
229910052681 coesite Inorganic materials 0.000 claims description 3
XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
229910052906 cristobalite Inorganic materials 0.000 claims description 3
239000000377 silicon dioxide Substances 0.000 claims description 3
235000012239 silicon dioxide Nutrition 0.000 claims description 3
229910052682 stishovite Inorganic materials 0.000 claims description 3
229910052905 tridymite Inorganic materials 0.000 claims description 3
JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
239000005750 Copper hydroxide Substances 0.000 claims description 2
229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 2
UXIJQZSBOOKEKZ-UHFFFAOYSA-N oxocopper hydrate Chemical compound O.[Cu]=O UXIJQZSBOOKEKZ-UHFFFAOYSA-N 0.000 claims description 2
SCZMHJCEJAGXRV-UHFFFAOYSA-K titanium(4+);phosphate Chemical compound [Ti+4].[O-]P([O-])([O-])=O SCZMHJCEJAGXRV-UHFFFAOYSA-K 0.000 abstract 1
235000021317 phosphate Nutrition 0.000 description 18
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
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 9
229910000165 zinc phosphate Inorganic materials 0.000 description 9
238000007792 addition Methods 0.000 description 8
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
238000004519 manufacturing process Methods 0.000 description 6
239000011734 sodium Substances 0.000 description 6
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
238000004140 cleaning Methods 0.000 description 5
229910052802 copper Inorganic materials 0.000 description 5
235000011007 phosphoric acid Nutrition 0.000 description 5
239000000243 solution Substances 0.000 description 5
229910002651 NO3 Inorganic materials 0.000 description 4
239000002202 Polyethylene glycol Substances 0.000 description 4
UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
229910000147 aluminium phosphate Inorganic materials 0.000 description 4
239000000203 mixture Substances 0.000 description 4
229920001223 polyethylene glycol Polymers 0.000 description 4
229920000642 polymer Polymers 0.000 description 4
LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
229910001420 alkaline earth metal ion Inorganic materials 0.000 description 3
150000001875 compounds Chemical class 0.000 description 3
230000000694 effects Effects 0.000 description 3
150000002170 ethers Chemical class 0.000 description 3
238000007654 immersion Methods 0.000 description 3
150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
-1 poly (aldehyde carboxylic acids Chemical class 0.000 description 3
239000002002 slurry Substances 0.000 description 3
229910052708 sodium Inorganic materials 0.000 description 3
229910000029 sodium carbonate Inorganic materials 0.000 description 3
235000017550 sodium carbonate Nutrition 0.000 description 3
101100172892 Caenorhabditis elegans sec-8 gene Proteins 0.000 description 2
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
239000007864 aqueous solution Substances 0.000 description 2
229910021538 borax Inorganic materials 0.000 description 2
239000011248 coating agent Substances 0.000 description 2
238000001816 cooling Methods 0.000 description 2
229920001577 copolymer Polymers 0.000 description 2
238000007598 dipping method Methods 0.000 description 2
BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
229910000397 disodium phosphate Inorganic materials 0.000 description 2
235000019800 disodium phosphate Nutrition 0.000 description 2
230000006872 improvement Effects 0.000 description 2
238000001000 micrograph Methods 0.000 description 2
239000002574 poison Substances 0.000 description 2
231100000614 poison Toxicity 0.000 description 2
239000000047 product Substances 0.000 description 2
235000017557 sodium bicarbonate Nutrition 0.000 description 2
229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
235000010288 sodium nitrite Nutrition 0.000 description 2
NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
229910052911 sodium silicate Inorganic materials 0.000 description 2
235000010339 sodium tetraborate Nutrition 0.000 description 2
238000005507 spraying Methods 0.000 description 2
238000003756 stirring Methods 0.000 description 2
BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
229920001353 Dextrin Polymers 0.000 description 1
239000004375 Dextrin Substances 0.000 description 1
229920005682 EO-PO block copolymer Polymers 0.000 description 1
108010010803 Gelatin Proteins 0.000 description 1
229910003708 H2TiF6 Inorganic materials 0.000 description 1
239000004115 Sodium Silicate Substances 0.000 description 1
229920002472 Starch Polymers 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
239000012190 activator Substances 0.000 description 1
239000000654 additive Substances 0.000 description 1
125000000217 alkyl group Chemical group 0.000 description 1
229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
125000000129 anionic group Chemical group 0.000 description 1
239000003945 anionic surfactant Substances 0.000 description 1
150000001450 anions Chemical class 0.000 description 1
239000003788 bath preparation Substances 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
150000001642 boronic acid derivatives Chemical class 0.000 description 1
BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
150000004649 carbonic acid derivatives Chemical class 0.000 description 1
150000001768 cations Chemical class 0.000 description 1
238000009833 condensation Methods 0.000 description 1
230000005494 condensation Effects 0.000 description 1
239000007859 condensation product Substances 0.000 description 1
229910000365 copper sulfate Inorganic materials 0.000 description 1
ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
230000007797 corrosion Effects 0.000 description 1
239000008367 deionised water Substances 0.000 description 1
229910021641 deionized water Inorganic materials 0.000 description 1
230000001687 destabilization Effects 0.000 description 1
239000003599 detergent Substances 0.000 description 1
235000019425 dextrin Nutrition 0.000 description 1
238000001035 drying Methods 0.000 description 1
238000010292 electrical insulation Methods 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
229920000159 gelatin Polymers 0.000 description 1
239000008273 gelatin Substances 0.000 description 1
235000019322 gelatine Nutrition 0.000 description 1
235000011852 gelatine desserts Nutrition 0.000 description 1
150000004676 glycans Chemical class 0.000 description 1
229910001385 heavy metal Inorganic materials 0.000 description 1
PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
150000004679 hydroxides Chemical class 0.000 description 1
239000008235 industrial water Substances 0.000 description 1
238000011835 investigation Methods 0.000 description 1
238000004898 kneading Methods 0.000 description 1
238000002156 mixing Methods 0.000 description 1
229910021527 natrosilite Inorganic materials 0.000 description 1
MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
239000002736 nonionic surfactant Substances 0.000 description 1
239000003921 oil Substances 0.000 description 1
238000004806 packaging method and process Methods 0.000 description 1
239000003973 paint Substances 0.000 description 1
239000002245 particle Substances 0.000 description 1
229940044654 phenolsulfonic acid Drugs 0.000 description 1
125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
150000003009 phosphonic acids Chemical class 0.000 description 1
229920001184 polypeptide Polymers 0.000 description 1
229920001451 polypropylene glycol Polymers 0.000 description 1
229920001282 polysaccharide Polymers 0.000 description 1
239000005017 polysaccharide Substances 0.000 description 1
150000003112 potassium compounds Chemical class 0.000 description 1
238000002203 pretreatment Methods 0.000 description 1
239000011164 primary particle Substances 0.000 description 1
102000004196 processed proteins & peptides Human genes 0.000 description 1
108090000765 processed proteins & peptides Proteins 0.000 description 1
239000002994 raw material Substances 0.000 description 1
230000009467 reduction Effects 0.000 description 1
239000008237 rinsing water Substances 0.000 description 1
230000005070 ripening Effects 0.000 description 1
239000012266 salt solution Substances 0.000 description 1
238000004062 sedimentation Methods 0.000 description 1
150000004760 silicates Chemical class 0.000 description 1
235000019795 sodium metasilicate Nutrition 0.000 description 1
239000001488 sodium phosphate Substances 0.000 description 1
235000019832 sodium triphosphate Nutrition 0.000 description 1
235000019698 starch Nutrition 0.000 description 1
239000008107 starch Substances 0.000 description 1
239000008399 tap water Substances 0.000 description 1
235000020679 tap water Nutrition 0.000 description 1
229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
238000004065 wastewater treatment Methods 0.000 description 1
229920001285 xanthan gum Polymers 0.000 description 1
239000010457 zeolite Substances 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

the invention relates to an activation agent based on titanium IV phosphate for the activation of metal surfaces prior to zinc phosphating and its use for the preparation of activation baths.
zinc phosphate layers can be produced on numerous metallic surfaces, such as iron, steel, galvanized alloy steel, aluminum or aluminized steel.
the zinc phosphate layers obtained serve to protect against corrosion, paint adhesion, reduction of sliding resistance, relief of cold forming and electrical insulation.
a phosphating process also includes various pre-treatment and post-treatment stages. It is essential to clean the metal surface, which is generally done with alkaline or acidic cleaners and removes oils, greases, oxides and adhering solid particles from the metal surface. If cleaning is carried out with mildly alkaline cleaners, it is in principle possible to combine cleaning with activation of the metal surface. As a rule, however, the activation follows the cleaning as a separate process step.
the task of activating the metal surface is to form a with the shortest possible phosphating times to ensure the finest possible crystalline zinc phosphate layer.
a criterion for the effectiveness of an activating agent is therefore the minimum phosphating time.
the suitability for forming even finely crystalline zinc phosphate layers can be determined on the basis of the layer weights or by scanning electron microscope images.
Titan IV phosphates form when aqueous titanium IV salt solutions are reacted with soluble phosphates or phosphoric acid.
products with activating properties are only obtained under special manufacturing conditions, which are described, for example, in US Pat. Nos. 2,310,239 and 2,456,947 and provide precise information regarding the type and concentration of the raw materials, temperature and pH range during manufacture.
the reaction conditions are kept constant, fluctuations in the application-technical effects are obtained from batch to batch.
activation agents based on titanium IV phosphate have to be prepared with deionized water.
the reason for this is that the alkaline earth metal ions present in the tap water as hardening agents destabilize titanium IV phosphate in activation baths.
These alkaline earth metal ions can also be introduced into the activation bath by rinsing water.
DE-A-3731089 proposes to activate cation-exchanging zeolites with a primary particle diameter of ⁇ 3 ⁇ m Mix in titanium phosphate.
Another way to improve the activation baths is described in EP-B-180523.
the addition of phosphonic acid acting as a complexing agent into the activation bath permits the use of industrial water for the bath preparation.
the phosphonic acid is said to cause the zinc phosphate layer to become extremely fine crystalline.
a serious disadvantage of individual phosphonic acids, however, is that they act as a phosphating bath poison even in concentrations of a few mg / l. An entry of phosphonic acid from the activation bath into the phosphating bath can render the phosphating bath unusable in a very short time.
DE-A-3814287 provides for the addition of poly (aldehyde carboxylic acids) in substoichiometric amounts as complexing agents for titanium IV during the production of activating titanium IV phosphates.
the introduction of the poly (aldehyde carboxylic acids) into the phosphating bath can have considerable disadvantages.
the object of the invention is an activation agent based on titanium IV phosphate for the activation of To provide metal surfaces before zinc phosphating, which does not have the disadvantages of the known activating agents, is easy to manufacture and, when used in the preparation of activating baths, leads to stable activating baths with a long service life, which also guarantee the formation of fine crystalline zinc phosphate layers in a short time.
the copper content was adjusted by adding copper compounds. These compounds have the effect that the minimum phosphating time is reduced considerably.
the addition of copper also means that the activation bath is stable over a wide temperature range and shows very good activating properties.
the activating agent contains copper compounds introduced via copper hydroxide, copper oxide hydrate, copper tartrate, copper nitrate and / or copper phosphate. Copper sulfate or copper chloride can be used but are not preferred.
Another advantageous embodiment of the invention consists in formulating an activating agent that contains an additional content of at least one of the components has condensed phosphate, silicate, complexing agent, water-soluble organic polymer, thickener and surfactant.
the additional additives to the activating agent mentioned here provide a number of additional advantageous properties when used as an activating bath.
the addition of condensed phosphate to the activating agent has the effect that the activating bath produced therefrom reacts less sensitively to introduced hardness formers.
Water-soluble organic polymer stabilizes the titanium IV phosphate dispersed in the activation bath in colloidal form and thus extends the service life of the activation bath considerably.
Surfactants reduce the surface tension, so that the activating titanium phosphate adheres better to the metal surface.
the activating agent contains 0.1 to 4% by weight of titanium phosphate (calculated as Ti).
activating agent for the preparation of aqueous activating baths for the activation of iron, steel, galvanized steel, galvanized alloy steel, aluminized steel and aluminum before the zinc phosphating takes place in such a way that activating baths with contents 0.001 to 0.060 g / l Ti 0.020 to 1.2 g / l o-phosphate (calculated as P2O5) and 0.001 to 0.1 g / l Cu with a pH of 7 to 11, preferably 7.5 to 10, result.
Copper concentrations above 0.1 g / l should be avoided as they can lead to a disruption in the phosphating in the subsequent step.
the activating agents can also be incorporated into ready-to-use, aqueous alkaline cleaning baths or else into aqueous-liquid or solid concentrates which are diluted with water to produce the cleaning baths. Because of its easy dilutability, the production of a liquid cleaner / activating agent is particularly advantageous.
alkaline cleaners for example, one or more compounds from the group of carbonates, silicates, phosphates, borates, hydroxides, hydroxycarboxylic acids and organic polymers such as sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), sodium metasilicate anhydrous (Na2SiO3), sodium disilicate (Na2Si2O5), sodium silicate, disodium phosphate (Na2HPO4), sodium tripolyphosphate (Na5P3O12B), sodium oxoateon, sodium borate Na sodium borate Bor , the trisodium salt of nitrilotriacetic acid, phenolsulfonic acid or naphthalenesulfonic acid-formaldehyde condensation products or - because of the better solubility in water - the corresponding potassium compounds.
NaHCO3 sodium carbonate
Na2CO3 sodium carbonate
Na2SiO3 sodium metasilicate anhydrous
Alkaline cleaners or the alkaline cleaner concentrates usually contain surfactants.
Particularly suitable surfactants are anionic or nonionic surfactants, such as Sodium alkylbenzenesulfonates, sodium alkylsulfonates, alkylphenol polyethylene glycol ethers, alkylphenol polyethylene glycol polypropylene glycol ethers, alkyl polyethylene glycol ethers, alkylamine-polyethylene glycol abducts or block copolymers of ethylene oxide and propylene oxide.
the surfactant content is about 0.5 to 10%, preferably 0.5 to 4%.
thickeners preferably polymers of natural origin
Suitable polymers are, for example, polypeptides such as gelatin, or polysaccharides such as starch, xanthan or dextrins.
the polymer is expediently first completely dissolved in water and then the various detergent components. Then, if necessary, the surfactants are dissolved or finely dispersed with vigorous stirring, and the activating agent is added last.
activating alkaline cleaner concentrate between 0 and 35 ° C is stable for several months and pumpable.
An activating agent was produced as described in the activating agent 1 process, but without the addition of copper nitrate.
activating agent was produced which corresponded to activating agent 2 in terms of composition, but did not contain any copper phosphate.
Activating agent 1 was used as activating agent 3, to which maleic anhydride copolymer was added in such a way that the resulting activating bath contained 10 mg / l.
Activating agent 1 which was mixed with surfactant in such quantities that the surfactant concentration of 0.3 g / l was formed when the activation bath was prepared, also served as the starting product.
the degree of layer coverage was determined in percent. This value indicates the proportion of the metal surface that is provided with a closed zinc phosphate layer. The assessment was made visually. Furthermore, the layer weight of the phosphate coating was determined gravimetrically and the minimum phosphating times determined. The Minimum phosphating time is the minimum time required to form a closed phosphate layer. The crystallinity of the phosphate layers was checked using scanning electron microscope images at a magnification of 2000 times.
the activating agent according to the invention according to Examples 1, 2, 3 and 4 leads to a high, almost complete coverage of the metal surface after only 3 minutes of phosphating time or enables short treatment times in the subsequent phosphating step.
the weight of the phosphate layer is well within the usual range.
the results for the activating agents 3 and 4 show that the addition of maleic anhydride copolymer or of surfactant, if the short minimum phosphating time (cf. activating agent 1) is observed, leads to a considerable increase in the service life of the activating bath.
the investigations with the scanning electron microscope showed that the phosphate layers obtained using the activating agents according to the invention were of fine-grained nature.

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Chemical & Material Sciences (AREA)
General Chemical & Material Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Engineering & Computer Science (AREA)
Materials Engineering (AREA)
Mechanical Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Chemical Treatment Of Metals (AREA)
Detergent Compositions (AREA)
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EP91200844A 1990-04-21 1991-04-11 Procédé pour appliquer des couches de phosphates sur des surfaces métalliques Expired - Lifetime EP0454211B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE4012795		1990-04-21
DE4012795A DE4012795A1 (de)	1990-04-21	1990-04-21	Aktivierungsmittel fuer die phosphatierung

Publications (2)

Publication Number	Publication Date
EP0454211A1 true EP0454211A1 (fr)	1991-10-30
EP0454211B1 EP0454211B1 (fr)	1994-06-22

Family

ID=6404842

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP91200844A Expired - Lifetime EP0454211B1 (fr)	1990-04-21	1991-04-11	Procédé pour appliquer des couches de phosphates sur des surfaces métalliques

Country Status (9)

Country	Link
US (1)	US5160551A (fr)
EP (1)	EP0454211B1 (fr)
JP (1)	JP3063921B2 (fr)
AT (1)	ATE107711T1 (fr)
BR (1)	BR9101616A (fr)
CA (2)	CA2040859C (fr)
DE (2)	DE4012795A1 (fr)
ES (1)	ES2055518T3 (fr)
ZA (1)	ZA912943B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0554179A1 (fr) *	1992-01-29	1993-08-04	C F P I	Concentré pour bain d'activation et d'affinage et bain obtenu à partir de ce concentré
WO1995031588A1 (fr) *	1994-05-11	1995-11-23	Henkel Kommanditgesellschaft Auf Aktien	Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes
US5503733A (en) *	1992-09-28	1996-04-02	Henkel Kommanditgesellschaft Auf Aktien	Process for phosphating galvanized steel surfaces
DE102008047533A1 (de)	2008-09-16	2010-04-15	Sachtleben Chemie Gmbh	Verfahren zur Herstellung von Titan-IV-phosphat
WO2010066765A1 (fr) *	2008-12-09	2010-06-17	Chemetall Gmbh	Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation
WO2014124866A1 (fr)	2013-02-13	2014-08-21	Chemetall Gmbh	Procédé permettant le revêtement de surfaces métalliques pour éviter la formation de piqûres sur des surfaces métalliques contenant du zinc
WO2015155163A3 (fr) *	2014-04-11	2015-12-17	Thyssenkrupp Steel Europe Ag	Procédé d'activation de surfaces métalliques à phosphater, de préférence de tôle d'acier galvanisée
EP2731730B1 (fr)	2011-07-15	2016-04-27	Dürr Systems GmbH	Installation pour le traitement de surface de pièces
EP4339324A1 (fr) *	2022-09-19	2024-03-20	ThyssenKrupp Steel Europe AG	Produit plat en acier doté d'une couche d'activation pour le formage à chaud

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US5628838A (en) *	1992-01-29	1997-05-13	C.F.P.I Societe Anonyme	Concentrate for activating and defining bath and bath obtained from this concentrate
US5494504A (en) *	1994-09-12	1996-02-27	Ppg Industries, Inc.	Liquid rinse conditioner for phosphate conversion coatings
JP3451334B2 (ja) *	1997-03-07	2003-09-29	日本パーカライジング株式会社	金属のりん酸塩皮膜化成処理前の表面調整用前処理液及び表面調整方法
MY129412A (en) *	1998-07-21	2007-03-30	Nihon Parkerizing	Conditioning liquid and conditioning process used in pretreatment for formation of phosphate layer on the metallic surface
JP2007204835A (ja) *	2006-02-03	2007-08-16	Nippon Paint Co Ltd	表面調整用組成物及び表面調整方法
CN103741132B (zh) *	2014-01-10	2016-08-17	湖南金裕化工有限公司	胶钛表面调整剂及其制备方法
CN121006536A (zh) *	2017-08-31	2025-11-25	凯密特尔有限责任公司	用于无镍磷化金属表面的改进方法
DE102018216216A1 (de) *	2018-09-24	2020-03-26	Thyssenkrupp Ag	Verfahren zur Verbesserung der Phosphatierbarkeit von metallischen Oberflächen, welche mit einer temporären Vor- bzw. Nachbehandlung versehen werden
DE102019134298A1 (de) *	2019-12-13	2021-06-17	Thyssenkrupp Steel Europe Ag	Verfahren zum Herstellen eines Stahlflachprodukts mit einer metallischen Schutzschicht auf Basis von Zink und einer auf einer Oberfläche der metallischen Schutzschicht erzeugten Phosphatierschicht und derartiges Stahlflachprodukt
CN114990537B (zh) *	2022-08-04	2022-11-25	山东一立动力科技股份有限公司	一种铝合金表面磷化处理方法
EP4689227A2 (fr) *	2023-04-04	2026-02-11	Chemetall GmbH	Composition de nettoyage et procédé de nettoyage de surfaces métalliques pour empêcher la corrosion d'un bain de rinçage

Citations (1)

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FR2114874A5 (fr) *	1970-11-19	1972-06-30	Dulux Australia Ltd

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BE410815A (fr) *	1934-08-13
US2329065A (en) *	1942-03-06	1943-09-07	Westinghouse Electric & Mfg Co	Corrosion resistant coating for metal surfaces
US3166444A (en) *	1962-04-26	1965-01-19	Lubrizol Corp	Method for cleaning metal articles
JPS5591997A (en) *	1978-12-30	1980-07-11	Nippon Parkerizing Co Ltd	Surface treating method of steel plate
DE3814363A1 (de) *	1988-04-28	1989-11-09	Henkel Kgaa	Titanfreie aktivierungsmittel, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung

1990
- 1990-04-21 DE DE4012795A patent/DE4012795A1/de not_active Withdrawn
1991
- 1991-04-11 AT AT91200844T patent/ATE107711T1/de not_active IP Right Cessation
- 1991-04-11 DE DE59101978T patent/DE59101978D1/de not_active Expired - Fee Related
- 1991-04-11 ES ES91200844T patent/ES2055518T3/es not_active Expired - Lifetime
- 1991-04-11 EP EP91200844A patent/EP0454211B1/fr not_active Expired - Lifetime
- 1991-04-17 US US07/686,825 patent/US5160551A/en not_active Expired - Lifetime
- 1991-04-19 CA CA002040859A patent/CA2040859C/fr not_active Expired - Fee Related
- 1991-04-19 ZA ZA912943A patent/ZA912943B/xx unknown
- 1991-04-19 CA CA002040872A patent/CA2040872A1/fr not_active Abandoned
- 1991-04-22 BR BR919101616A patent/BR9101616A/pt unknown
- 1991-04-22 JP JP3118013A patent/JP3063921B2/ja not_active Expired - Fee Related

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR2114874A5 (fr) *	1970-11-19	1972-06-30	Dulux Australia Ltd

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Band 4, Nr. 144 (C-27)[626], 11. Oktober 1980; & JP-A-55 091 997 (NIPPON PARKERIZING K.K.) 11-07-1980 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0554179A1 (fr) *	1992-01-29	1993-08-04	C F P I	Concentré pour bain d'activation et d'affinage et bain obtenu à partir de ce concentré
US5503733A (en) *	1992-09-28	1996-04-02	Henkel Kommanditgesellschaft Auf Aktien	Process for phosphating galvanized steel surfaces
WO1995031588A1 (fr) *	1994-05-11	1995-11-23	Henkel Kommanditgesellschaft Auf Aktien	Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes
DE102008047533A1 (de)	2008-09-16	2010-04-15	Sachtleben Chemie Gmbh	Verfahren zur Herstellung von Titan-IV-phosphat
US9364855B2 (en)	2008-12-09	2016-06-14	Chemetall Gmbh	Method for coating metal surfaces with an activating agent prior to phosphating
US9358574B2 (en)	2008-12-09	2016-06-07	Chemetall Gmbh	Method for coating metal surfaces with an activating agent prior to phosphating
WO2010066765A1 (fr) *	2008-12-09	2010-06-17	Chemetall Gmbh	Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation
CN106947967A (zh) *	2008-12-09	2017-07-14	凯密特尔有限责任公司	在磷化之前用活化剂涂覆金属表面的方法
CN106947967B (zh) *	2008-12-09	2020-07-03	凯密特尔有限责任公司	在磷化之前用活化剂涂覆金属表面的方法
EP2731730B1 (fr)	2011-07-15	2016-04-27	Dürr Systems GmbH	Installation pour le traitement de surface de pièces
WO2014124866A1 (fr)	2013-02-13	2014-08-21	Chemetall Gmbh	Procédé permettant le revêtement de surfaces métalliques pour éviter la formation de piqûres sur des surfaces métalliques contenant du zinc
WO2015155163A3 (fr) *	2014-04-11	2015-12-17	Thyssenkrupp Steel Europe Ag	Procédé d'activation de surfaces métalliques à phosphater, de préférence de tôle d'acier galvanisée
US10480080B2 (en)	2014-04-11	2019-11-19	Thyssenkrupp Steel Europe Ag	Method for activating metal surfaces to be phosphated
EP4339324A1 (fr) *	2022-09-19	2024-03-20	ThyssenKrupp Steel Europe AG	Produit plat en acier doté d'une couche d'activation pour le formage à chaud

Also Published As

Publication number	Publication date
US5160551A (en)	1992-11-03
CA2040859A1 (fr)	1991-10-22
JPH04254589A (ja)	1992-09-09
DE4012795A1 (de)	1991-10-24
EP0454211B1 (fr)	1994-06-22
ES2055518T3 (es)	1994-08-16
JP3063921B2 (ja)	2000-07-12
ZA912943B (en)	1992-12-30
ATE107711T1 (de)	1994-07-15
CA2040872A1 (fr)	1991-10-22
DE59101978D1 (de)	1994-07-28
BR9101616A (pt)	1991-12-10
CA2040859C (fr)	2000-11-21

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Publication	Publication Date	Title
EP0454211A1 (fr)	1991-10-30	Procédé pour appliquer des couches de phosphates sur des surfaces métalliques
DE3879099T2 (de)	1993-07-15	Verfahren und zusammensetzung zur herstellung von zinkphosphatueberzuegen.
DE1937841C3 (de)	1979-07-12	Verfahren zur Reinigung von Aluminium-Oberflächen vor dem Lackieren
DE2904402A1 (de)	1979-10-25	Phosphatierungsmittel
EP0240943B1 (fr)	1990-10-10	Procédé pour appliquer des couches de conversion sur des surfaces de zinc ou de ses alliages
EP1254279A2 (fr)	2002-11-06	Anticorrosif et procede de protection contre la corrosion destine a des surfaces metalliques
EP3676419B1 (fr)	2023-10-11	Procédé amélioré de phosphatage sans nickel des surfaces métalliques
DE69404663T2 (de)	1997-11-27	Vorspülung für die phosphatierung von oberflächen aus metall
DE2902916A1 (de)	1980-02-21	Verfahren zur herstellung von titanium enthaltenden phosphaten als konditionierungsmittel fuer metalloberflaechen
EP0760870B1 (fr)	1998-10-28	Phosphatation ferrique a l'aide d'acides monocarboxyliques substitues
DE4031817A1 (de)	1992-04-09	Verfahren zur passivierenden nachbehandlung von phosphatierten metalloberflaechen
EP0039093B1 (fr)	1983-11-16	Procédé de phosphatation des surfaces de métaux et application de ce procédé
DE2315180A1 (de)	1973-11-08	Phosphatierungsloesung
DE3875459T2 (de)	1993-03-25	Verfahren zum phosphatieren von metalloberflaechen.
EP0031103B1 (fr)	1983-09-28	Procédé pour le traitement préliminaire de surfaces métalliques avant la phosphatation
DE974713C (de)	1961-04-06	Verfahren zur Herstellung von UEberzuegen auf Metallen
DE1521889B1 (de)	1972-01-13	Verfahren zur phosphatierung von eisen und stahl
DE3009931C2 (de)	1986-04-03	Mittel zum Schützen von Stahloberflächen
DE69513036T3 (de)	2004-04-22	Flüssiges Aktivierungsmittel für Phosphat-Konversionsüberzügen
DE102005047424A1 (de)	2007-04-05	Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren
EP0121274A1 (fr)	1984-10-10	Procédé de phosphatation de surfaces métalliques
EP0340530B1 (fr)	1992-06-24	Agents d'activation ne contenant pas de titane, procédé pour leur préparation et leur utilisation pour activer des surfaces métalliques avant la phosphatation au zinc
DE2239581A1 (de)	1973-03-15	Loesung und verfahren zum aufbringen von ueberzuegen auf zink oder zinklegierungen
EP0454212A1 (fr)	1991-10-30	Procédé pour préparer des agents activateurs pour la phosphatation au zinc et leur utilisation
DE3922464A1 (de)	1990-01-11	Waessrige schmierbehandlungsfluessigkeit und verfahren zur kalten, plastischen bearbeitung metallischer materialien