EP0069950B1 - Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen - Google Patents
Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen Download PDFInfo
- Publication number
- EP0069950B1 EP0069950B1 EP82105960A EP82105960A EP0069950B1 EP 0069950 B1 EP0069950 B1 EP 0069950B1 EP 82105960 A EP82105960 A EP 82105960A EP 82105960 A EP82105960 A EP 82105960A EP 0069950 B1 EP0069950 B1 EP 0069950B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal surfaces
- contact
- brought
- phosphating solution
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 33
- 229910052751 metal Inorganic materials 0.000 title claims description 22
- 239000002184 metal Substances 0.000 title claims description 22
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 12
- -1 aromatic nitro-compound Chemical class 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims 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 claims description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 7
- 150000002828 nitro derivatives Chemical class 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 5
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 claims description 2
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 29
- 150000002500 ions Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- 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 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- YIVJSMIYMAOVSJ-UHFFFAOYSA-N sodium;phosphono dihydrogen phosphate Chemical compound [Na+].OP(O)(=O)OP(O)(O)=O YIVJSMIYMAOVSJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 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 1
- 238000004448 titration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide 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
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-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
- 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
- C23C22/362—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 also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
Definitions
- the invention relates to a method for applying phosphate coatings on metal surfaces by means of phosphating solutions based on zinc phosphate as an essential layer-forming component, which are accelerated with chlorate and water-soluble aromatic nitro compound.
- Oxidizing agents such as chlorate, nitrate, nitrite, hydrogen peroxide or peroxy compounds in general and organic nitro compounds in particular play an important role as accelerators.
- DE-OS 3 016 576 describes a phosphating process based on zinc phosphate solution which contains nitrate and chlorate as accelerators. In a process based on zinc phosphate solution, it is also intended to use chlorate, nitrite, nitrate, organic nitro compounds or mixtures thereof (AT-PS 314 931).
- GB-PS 1 542 222 provides for the use of chlorate and nitrobenzenesulfonate as accelerators in zinc phosphate processes.
- the weight ratio of chlorate to nitrobenzenesulfonate should be 3: 1 to 5: 1.
- DE-OS 3 004927 also describes a process for phosphating metal surfaces with zinc phosphate solutions, which may contain nitrite and / or organic nitro compound and optionally additionally chlorate.
- the amounts of nitrite should be 0.01 to 0.2 g / l
- the amounts of organic nitro compound and optionally chlorate should be in the range of 0.05 to 2 g / l.
- the object of the invention is to provide a method for applying phosphate layers on metal surfaces which does not have the known, in particular the aforementioned disadvantages, is simple to carry out and can do without the use of expensive chemicals.
- the method according to the invention is particularly suitable for producing phosphate coatings on steel, galvanized steel and aluminum or on surfaces which contain several of these metals.
- the active bath components can be introduced in the form of water-soluble or acid-soluble salts or compounds or as acids in water.
- the water-soluble aromatic nitro compound should have no more than two nitro groups.
- nitrobenzoic acid is suitable.
- nitrobenzenesulfonate in particular m-nitrobenzenesulfonate, is used as the water-soluble aromatic nitro compound.
- solutions used to produce the phosphate coating can have further components if necessary. So it is z. B. advantageous to bring solutions with the metal surfaces in contact, which additionally contain 2 to 9 g / I NOa.
- phosphating solutions that additionally contain 0.2 to 4 g / 1 fluoride ions.
- the fluoride can be present in the phosphating solution as free or as a complex-bound fluorine ion.
- Suitable complex fluorides are e.g. B. fluoborates and / or fluosilicates.
- phosphating solutions which contain an additional content of Ni, Co and / or Fe ions are advantageous. These ions should preferably be present in a total amount of 0.1 to 2.5 g / l. Such additives can expediently be used in conjunction with 0.2 to 4 g / l of the aforementioned simple or complex fluorides. Such phosphating solutions with contents of Ni, Co and / or Fe ions as well as simple and / or complex fluorine ions are also suitable for the treatment of several metals existing surfaces an advantage. Fluorine contents of up to 1 g / l are generally sufficient. When measuring the addition of Ni, Co and / or Fe ions, the total of these should not exceed the Zn ion content of the phosphating solution.
- a phosphating solution which has a pH of 2 to 3.5, preferably 2.9 to 3.2.
- the phosphating solution should have 5 to 30 points total acid and 0.3 to 2.5 points free acid.
- the number of points is defined in the usual way. For example, the amount of 0.1 n sodium hydroxide solution (in ml) consumed before the bromphenol blue is handled is equal to the number of free acid and the consumption when handling phenolphthalein is equal to the total acid score. The number of points can also be determined by potentiometric titration.
- the phosphating solution can be applied in any manner. Dip and spray treatments as well as combined dip / spray treatments are particularly suitable.
- the duration of exposure depends on the desired phosphate layer formation and on the process conditions, but also on the nature of the metal surface and the preceding treatment.
- the treatment times are generally in the range from 0.5 to 3 minutes.
- layer weights of about 0.86 to 1.60 g / m 2 (for steel), from 1.30 to 2.15 g / m 2 (for galvanized steel) and up to 0.43 g / m 2 (with aluminum) adjustable.
- the respective value results from the accelerator ratio used, the layer weight decreasing as the proportion of aromatic nitro compound increases.
- the phosphating solution used in carrying out the process according to the invention is usually prepared from a concentrate and diluted accordingly.
- the free acid content in the concentrate can be set sufficiently high to reliably avoid solid separation during storage or transport.
- the appropriate pH or the free acid content is then set.
- the working phosphating solution can be supplemented using a supplementary solution which contains all the active ingredients or using several supplementary solutions which contain all of the active ingredients in their entirety.
- a supplemental solution may contain zinc and phosphate ions and optionally nitrate and / or fluoride and / or nickel ions and another supplementary solution may contain alkali ions, nitrobenzenesulfonate and chlorate ions.
- the process according to the invention is used within a customary process which consists of cleaning, water rinsing, formation of a phosphate layer, water rinsing, post-treatment and rinsing with demineralized water. This can be followed by a painting treatment or another type of coating.
- the process according to the invention is particularly advantageous as a pretreatment before electrocoating, especially cathodic electrocoating.
- the layers produced by the process according to the invention are very fine-grained and permit excellent anchoring of a lacquer coating applied subsequently.
- the phosphate coatings obtained offer good corrosion protection and show good physical properties, in particular if the subsequent painting is carried out by electrocoating, in particular by cathodic electrocoating, and steel surfaces, galvanized surfaces or aluminum are treated in the process.
- the method according to the invention is also characterized by reduced sludge and crust formation in the phosphating device.
- By changing the accelerator ratio it is finally possible to adapt the quality of the phosphate layer with regard to layer weight and fine grain to the respective requirements.
- Concentrate A was first prepared by mixing the following ingredients in a stainless steel container: In a second container, B mixed while stirring.
- the sheets treated in this way were cathodically dip-coated with an electrocoat material (ED 3002 R) from PPG Industries and subjected to the tests for determining the corrosion resistance and various physical properties.
- the properties determined in each case were excellent.
- Example 2 The procedure according to Example 2 was repeated, but hot-dip galvanized, re-rolled sheets were used instead of steel sheets. Similar test results as in Example 2 were obtained.
- Example 2 The procedure according to Example 2 was repeated. Instead of the steel sheets, aluminum sheets were treated. Test results similar to those of Example 2 were obtained.
- Examples 2 to 4 were carried out again, with the difference that the phosphating in stage 3.) according to Example 2 was carried out by immersion treatment at 49 ° C. for 1 minute.
- the sheet qualities treated in this way also showed test results similar to those in Examples 2 to 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/282,480 US4498935A (en) | 1981-07-13 | 1981-07-13 | Zinc phosphate conversion coating composition |
US282480 | 1981-07-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0069950A1 EP0069950A1 (de) | 1983-01-19 |
EP0069950B1 true EP0069950B1 (de) | 1985-10-23 |
Family
ID=23081699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82105960A Expired EP0069950B1 (de) | 1981-07-13 | 1982-07-03 | Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen |
Country Status (14)
Country | Link |
---|---|
US (1) | US4498935A (pt) |
EP (1) | EP0069950B1 (pt) |
JP (1) | JPS5819481A (pt) |
KR (1) | KR890001036B1 (pt) |
AU (1) | AU549517B2 (pt) |
BR (1) | BR8204044A (pt) |
CA (1) | CA1200471A (pt) |
DE (2) | DE3267010D1 (pt) |
ES (1) | ES513841A0 (pt) |
GB (1) | GB2102839A (pt) |
MX (1) | MX157371A (pt) |
PH (1) | PH19127A (pt) |
PT (1) | PT75220B (pt) |
ZA (1) | ZA824588B (pt) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3244715A1 (de) * | 1982-12-03 | 1984-06-07 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur phosphatierung von metalloberflaechen sowie hierfuer geeignete badloesungen |
DE3311738A1 (de) * | 1983-03-31 | 1984-10-04 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metalloberflaechen |
DE3325974A1 (de) * | 1983-07-19 | 1985-01-31 | Gerhard Collardin GmbH, 5000 Köln | Verfahren und universell anwendbare mittel zum beschleunigten aufbringen von phosphatueberzuegen auf metalloberflaechen |
GB2148950B (en) * | 1983-10-26 | 1987-02-04 | Pyrene Chemical Services Ltd | Phosphating composition and processes |
GB8329250D0 (en) * | 1983-11-02 | 1983-12-07 | Pyrene Chemical Services Ltd | Phosphating processes |
DE3407513A1 (de) * | 1984-03-01 | 1985-09-05 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur zink-calcium-phosphatierung von metalloberflaechen bei niedriger behandlungstemperatur |
DE3408577A1 (de) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metallen |
ES8606528A1 (es) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Procedimiento para el fosfatado de superficies metalicas, especialmente ferreas |
WO1986005094A1 (en) * | 1985-03-08 | 1986-09-12 | Takeda Chemical Industries, Ltd. | Antiobesity agent and composition |
WO1986006276A1 (en) * | 1985-04-30 | 1986-11-06 | Takeda Chemical Industries, Ltd. | Sugar digestion-restraining agent and sugar digestion-restraining composition |
GB8523572D0 (en) * | 1985-09-24 | 1985-10-30 | Pyrene Chemicals Services Ltd | Coating metals |
US4673445A (en) * | 1986-05-12 | 1987-06-16 | The Lea Manufacturing Company | Corrosion resistant coating |
DE3630246A1 (de) * | 1986-09-05 | 1988-03-10 | Metallgesellschaft Ag | Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung |
DE3631759A1 (de) * | 1986-09-18 | 1988-03-31 | Metallgesellschaft Ag | Verfahren zum erzeugen von phosphatueberzuegen auf metalloberflaechen |
US6551417B1 (en) | 2000-09-20 | 2003-04-22 | Ge Betz, Inc. | Tri-cation zinc phosphate conversion coating and process of making the same |
JP5462467B2 (ja) | 2008-10-31 | 2014-04-02 | 日本パーカライジング株式会社 | 金属材料用化成処理液および処理方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2295545A (en) * | 1938-02-04 | 1942-09-15 | Parker Rust Proof Co | Treatment of metal |
DE1287890B (pt) * | 1961-03-23 | 1900-01-01 | ||
US3272664A (en) * | 1963-07-25 | 1966-09-13 | Detrex Chem Ind | Composition and method for coating metal surfaces |
GB1542222A (en) * | 1977-01-06 | 1979-03-14 | Pyrene Chemical Services Ltd | Phosphate coating compositions |
JPS53138937A (en) * | 1977-05-11 | 1978-12-04 | Nippon Paint Co Ltd | Chemical treating method for iron phosphate film |
JPS5811513B2 (ja) * | 1979-02-13 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
DE3016576A1 (de) * | 1980-04-30 | 1981-11-05 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung |
-
1981
- 1981-07-13 US US06/282,480 patent/US4498935A/en not_active Expired - Fee Related
-
1982
- 1982-06-16 CA CA000405302A patent/CA1200471A/en not_active Expired
- 1982-06-17 AU AU84952/82A patent/AU549517B2/en not_active Ceased
- 1982-06-25 PH PH27500A patent/PH19127A/en unknown
- 1982-06-28 ZA ZA824588A patent/ZA824588B/xx unknown
- 1982-07-03 DE DE8282105960T patent/DE3267010D1/de not_active Expired
- 1982-07-03 DE DE19823224923 patent/DE3224923A1/de not_active Withdrawn
- 1982-07-03 EP EP82105960A patent/EP0069950B1/de not_active Expired
- 1982-07-08 GB GB08219750A patent/GB2102839A/en not_active Withdrawn
- 1982-07-09 ES ES513841A patent/ES513841A0/es active Granted
- 1982-07-09 PT PT75220A patent/PT75220B/pt not_active IP Right Cessation
- 1982-07-12 KR KR8203103A patent/KR890001036B1/ko active
- 1982-07-12 BR BR8204044A patent/BR8204044A/pt unknown
- 1982-07-13 MX MX193579A patent/MX157371A/es unknown
- 1982-07-13 JP JP57121949A patent/JPS5819481A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
AU8495282A (en) | 1983-01-20 |
MX157371A (es) | 1988-11-18 |
JPH0331790B2 (pt) | 1991-05-08 |
KR890001036B1 (ko) | 1989-04-20 |
ZA824588B (en) | 1983-05-25 |
DE3224923A1 (de) | 1983-02-17 |
BR8204044A (pt) | 1983-07-05 |
PT75220A (fr) | 1982-08-01 |
KR840000670A (ko) | 1984-02-25 |
EP0069950A1 (de) | 1983-01-19 |
AU549517B2 (en) | 1986-01-30 |
ES8305051A1 (es) | 1983-04-01 |
PH19127A (en) | 1986-01-08 |
DE3267010D1 (en) | 1985-11-28 |
ES513841A0 (es) | 1983-04-01 |
CA1200471A (en) | 1986-02-11 |
US4498935A (en) | 1985-02-12 |
JPS5819481A (ja) | 1983-02-04 |
PT75220B (fr) | 1984-07-23 |
GB2102839A (en) | 1983-02-09 |
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