EP0327153B1 - Procédé pour former des couches de phosphates sur des métaux - Google Patents
Procédé pour former des couches de phosphates sur des métaux Download PDFInfo
- Publication number
- EP0327153B1 EP0327153B1 EP89200142A EP89200142A EP0327153B1 EP 0327153 B1 EP0327153 B1 EP 0327153B1 EP 89200142 A EP89200142 A EP 89200142A EP 89200142 A EP89200142 A EP 89200142A EP 0327153 B1 EP0327153 B1 EP 0327153B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- individual parts
- solution
- process according
- ions
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 30
- 229910019142 PO4 Inorganic materials 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 28
- 239000010452 phosphate Substances 0.000 title claims description 27
- 238000000576 coating method Methods 0.000 title claims description 18
- 229910052751 metal Inorganic materials 0.000 title claims description 5
- 239000002184 metal Substances 0.000 title claims description 5
- 150000002739 metals Chemical class 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 235000021317 phosphate Nutrition 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- -1 nitrate ions Chemical class 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 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 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 7
- 230000009189 diving Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 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 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 229940005740 hexametaphosphate Drugs 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
- 230000002045 lasting effect Effects 0.000 description 1
- JCYPECIVGRXBMO-FOCLMDBBSA-N methyl yellow Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1 JCYPECIVGRXBMO-FOCLMDBBSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- 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
- C23C22/78—Pretreatment of the material to be coated
Definitions
- the invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces having individual parts made of metal by means of aqueous phosphating solutions containing zinc, phosphate, nitrate, fluoride, nickel, copper and autocatalytically formed nitrite ions and practically free of iron are II ions.
- Another type of zinc phosphate process which usually works with high nitrate contents and at higher temperatures, is characterized in that the phosphating solutions used are practically free of iron II ions. In them, nitrite, which contains the iron II ions, forms autocatalytically Iron III ions are transferred, which in turn form poorly soluble iron phosphate with phosphate ions (DE-A-25 40 684).
- the solutions used also contain 20 to 50 g / l nitrate, 0.001 to 0.5 g / l nickel, 0.001 to 0.050 g / l copper, 0.1 to 2.0 g / l fluoride and 0.01 to 0.5 g / l nitrite.
- the weight ratio of free P2O5 to total P2O5 should (0.30 to 0.65): 1, the application temperature 50 to 80 ° C.
- treatment times are 5 to 15 minutes. or from about 1 to 10 min. however, can often only be achieved with a comparatively large expenditure on equipment, d. H. it would be desirable to have procedures that can be performed in a shorter time. This is particularly desirable if the surface treatment in predetermined manufacturing processes that are used in the treatment of individual parts, eg. B. of the aforementioned type, are of importance, should be integrated.
- the object of the invention is to provide a method for producing phosphate coatings on individual parts having at least partially iron or steel surfaces To provide, which does not have the disadvantage of the long treatment time, but leads to phosphate coatings in a short time, which are nevertheless of high quality.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the individual parts are in contact with a phosphating solution at a temperature in the range from 60 to 100 ° C. for a period of 3 to 30 seconds brings that 10 to 80 g / l zinc 12 to 80 g / l phosphate (calculated as P2O5) 40 to 150 g / l nitrate as well as additional 0.1 to 5 g / l fluoride 0.01 to 10 g / l nickel 0.001 to 0.1 g / l copper contains, in which the ratio of free acid to total acid is set to (0.1 to 0.3): 1 and which has at least 80 points total acid.
- nitrite is formed autocatalytically, it may be necessary to add nitrite to the phosphating solution, for example in an amount of 0.03 to 0.2 g / l, in the initial phase of the process.
- the method according to the invention is used in particular for the treatment of individual parts whose iron or steel surface has alloy additions of up to a maximum of 5% by weight.
- the individual components of the phosphating solution such as zinc, phosphate, nitrate, etc.
- the individual components are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form.
- the individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution.
- additional cations from the alkali and / or ammonium group may have to be used.
- titrate 10 ml bath sample with n / 10 NaOH against the first or second change in phosphoric acid using the color change of dimethyl yellow (free acid) or phenolphthalein (total acid), for example, as an indicator.
- the ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.
- the content of nitrite points is usually determined using the saccharometer method. For this, 50 ml of bath solution are mixed with 2 to 5 g of sulfamic acid. The amount of gas generated in ml is equal to the number of points. A gas point corresponds to a content of 46 mg / l NO2 in the phosphating solution.
- the contact of the individual parts with the phosphating solution is preferably carried out by dipping or flooding.
- the phosphate coatings produced by the process according to the invention have a layer weight of 2.0 to 10 g / m2.
- a preferred embodiment of the invention consists in bringing the individual parts into contact with a phosphating solution 30 to 60 g / l zinc 30 to 50 g / l phosphate (calculated as P2O5) 65 to 100 g / l nitrate 0.5 to 3.0 g / l fluoride 0.02 to 0.5 g / l nickel and 0.001 to 0.1 g / l copper contains.
- the rate of formation of the phosphate coating can be increased if, in accordance with a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains further accelerating additives.
- accelerating additives can be, for example, chlorate, bromate, peroxide, m-nitrobenzenesulfonate, nitrophenol or combinations thereof.
- a further improvement in the properties of the phosphate coating can be achieved if, according to a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains an additional 0.1 to 10 g / l, preferably 1 to 5 g / l, of manganese.
- a phosphating solution which additionally contains 0.05 to 3 g / l tartaric acid and / or citric acid.
- Another advantageous embodiment of the invention is to clean the individual parts before phosphating, if necessary to free them of rust, scale and phosphate layer and to activate them, and to passivate them with a rinse solution after phosphating, each of the process steps lasting from 3 to 30 sec is carried out.
- an alkaline cleaning solution at a temperature in the range between 60 and 100 ° C. and a concentration in the range from 20 to 200 g / l for cleaning.
- cleaners those based on sodium hydroxide, gluconate, phosphate with an additional content of carbonate, silicate and borate and surfactant.
- the cleaner is preferably used in spraying.
- Sulfuric acid or phosphoric acid solutions at a temperature in the range from 60 to 100 ° C. and a concentration in the range from 5 to 50% by weight have proven to be advantageous for the removal of rust, scale and phosphate layers that may be required.
- a sulfuric or phosphoric acid is used which additionally contains iron II and / or iron III ions in a concentration in the range from 1 to 50 g / l.
- the phosphating treatment After the phosphating treatment, it is usually rinsed with water, rinsed if necessary and dried if necessary.
- a further advantageous embodiment of the invention provides for the individual parts to be passivated with a chrome-containing or chrome-free rinse solution. Possibly. can also be treated with an emulsion of an anti-corrosion oil, or it can be painted with or without passivation. In the event that cold forming is intended, an aftertreatment with a soap bath can also be carried out.
- the phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used.
- the phosphating process according to the invention is particularly favorable in improving the corrosion protection in the case of a subsequent painting.
- the phosphate coating produced after this operation had a basis weight of 4 to 5 g / m2.
- the phosphate coating was uniformly opaque and fine crystalline.
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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)
Claims (12)
- Procédé de formation de revêtements de phosphate sur des pièces métalliques détachées comportant au moins partiellement des surfaces de fer ou d'acier, au moyen de solutions aqueuses de phosphatation, qui contiennent des ions zinc, phosphate, nitrate, fluorure, nickel, cuivre et, formés par autocatalyse, nitrites et qui sont pratiquement exemptes d'ions fer II, caractérisé en ce qu'il consiste à mettre les pièces à une température de l'ordre de 60 à 100°C pendant une durée de 3 à 30 secondes en contact avec une solution de phosphatation, qui contient
de 10 à 80 g de zinc/l
de 12 à 80 g de phosphate (exprimés en P₂O₅)/l
de 40 à 150 g de nitrate/l ainsi qu'en plus
de 0,1 à 5 g de fluorure/l
de 0,01 à 10 g de nickel/l
de 0,001 à 0,1g de cuivre/l
le rapport de l'acidité libre à l'acidité totale étant réglé à (0,1 à 0,3):1 et l'acidité totale étant d'au moins 80 points. - Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à mettre les pièces détachées en contact avec une solution de phosphatation, qui contient
de 30 à 60 g de zinc/l
de 30 à 50 g de phosphate (exprimés en P₂O₅)/l
de 65 à 100 g de nitrate/l
de 0,5 à 3,0 g de fluorure/l
de 0,02 à 0,5 g de nickel/l et
de 0,001 à 0,1g de cuivre/l.
- Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'il consiste à mettre les pièces détachées en contact avec une solution de phosphatation qui contient des accélérateurs supplémentaires.
- Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce qu'il consiste à mettre les pièces détachées en contact avec une solution de phosphatation qui contient, en outre, de 0,1 à 10 g et, de préférence, de 1 à 5 g de manganèse/l.
- Procédé suivant la revendication 1, 2, 3 ou 4, caractérisé en ce qu'il consiste à mettre les pièces détachées en contact avec une solution de phosphatation qui contient, en outre, de 0,05 à 3 g d'acide tartrique et/ou d'acide citrique/l.
- Procédé suivant l'une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'il consiste à nettoyer les pièces détachées avant la phosphatation, à les débarrasser, le cas échéant, de la rouille, de la calamine et des couches de phosphate, à les activer et, après la phosphatation, à les passiver par une solution de postrinçage, chacun des stades du procédé étant effectué pendant une durée de 3 à 30 secondes.
- Procédé suivant la revendication 6, caractérisé en ce qu'il consiste, pour le nettoyage, à mettre les pièces détachées en contact avec une solution alcaline de nettoyage ayant une température de l'ordre de 60 et 100°C et une concentration de l'ordre de 20 à 200 g/l.
- Procédé suivant la revendication 6 ou 7, caractérisé en ce qu'il consiste à mettre les pièces détachées en contact avec une solution d'acide sulfurique ou une solution d'acide phosphorique d'une température de 60 à 100°C et d'une concentration de l'ordre de 5 à 50 % en poids.
- Procédé suivant la revendication 8, caractérisé en ce qu'il consiste à mettre les pièces détachées en contact avec une solution d'acide sulfurique ou d'acide phosphorique, qui contient en outre des ions de fer-II et/ou de fer-III en une concentration de l'ordre de 1 à 50 g/l.
- Procédé suivant la revendication 8 ou 9, caractérisé en ce qu'il consiste à mettre les pièces détachées, après le traitement par la solution d'acide sulfurique ou d'acide phosphorique, en contact avec une solution qui contient les mêmes acides en une concentration de l'ordre de 0,3 à 3 % en poids et qui a une température de 20 à 50°C.
- Procédé suivant l'une ou plusieurs des revendications 1 à 10, caractérisé en ce qu'il consiste à activer les pièces détachées par une dispersion qui est constituée d'une dispersion aqueuse de phosphate de titane et qui contient, le cas échéant, en plus des phosphates condensés.
- Procédé suivant l'une ou plusieurs des revendications 1 à 11, caractérisé en ce qu'il consiste à passiver les pièces détachées après l'apport du revêtement de phosphate par une solution de post-rinçage contenant du chrome ou exempte de chrome.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3803068 | 1988-02-03 | ||
DE3803068 | 1988-02-03 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0327153A2 EP0327153A2 (fr) | 1989-08-09 |
EP0327153A3 EP0327153A3 (en) | 1990-04-25 |
EP0327153B1 true EP0327153B1 (fr) | 1993-08-04 |
Family
ID=6346467
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89200142A Expired - Lifetime EP0327153B1 (fr) | 1988-02-03 | 1989-01-24 | Procédé pour former des couches de phosphates sur des métaux |
Country Status (6)
Country | Link |
---|---|
US (1) | US4950339A (fr) |
EP (1) | EP0327153B1 (fr) |
JP (1) | JP2713334B2 (fr) |
CA (1) | CA1330515C (fr) |
DE (1) | DE58905074D1 (fr) |
ES (1) | ES2058464T3 (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3913089A1 (de) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten |
DE4433946A1 (de) * | 1994-09-23 | 1996-03-28 | Henkel Kgaa | Phosphatierverfahren ohne Nachspülung |
DE19639597C2 (de) * | 1996-09-26 | 2000-01-20 | Henkel Kgaa | Verfahren zur Phosphatierung von laufenden Bändern aus kalt- oder warmgewalztem Stahl in schnellaufenden Bandanlagen |
US5954892A (en) * | 1998-03-02 | 1999-09-21 | Bulk Chemicals, Inc. | Method and composition for producing zinc phosphate coatings on metal surfaces |
JP3479609B2 (ja) | 1999-03-02 | 2003-12-15 | 日本パーカライジング株式会社 | スラッジ発生のないリン酸亜鉛処理液およびリン酸亜鉛処理方法 |
JP4630326B2 (ja) * | 1999-08-09 | 2011-02-09 | 新日本製鐵株式会社 | 加工性に優れたリン酸塩処理亜鉛系めっき鋼板の製造方法 |
JP2001170557A (ja) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | めっき鋼板用表面処理液およびその処理方法 |
DE10010355A1 (de) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile |
US6530999B2 (en) | 2000-10-10 | 2003-03-11 | Henkel Corporation | Phosphate conversion coating |
US20060108016A1 (en) * | 2002-07-31 | 2006-05-25 | Shinichi Funatsu | Resin-lined steel pipe and method for production thereof |
CA2902066C (fr) | 2013-03-06 | 2018-01-02 | Quaker Chemical Corporation | Revetement de conversion a haute temperature sur des substrats en acier et en fer |
CN105543822A (zh) * | 2015-12-31 | 2016-05-04 | 芜湖市金宇石化设备有限公司 | 一种用于汽车车门涂装前磷化处理的处理液 |
CN105603406A (zh) * | 2015-12-31 | 2016-05-25 | 芜湖市金宇石化设备有限公司 | 一种用于汽车车门涂装前磷化处理的处理液的制备方法 |
CN105463422A (zh) * | 2015-12-31 | 2016-04-06 | 芜湖市金宇石化设备有限公司 | 一种汽车车门涂装前磷化处理方法 |
CN111197163A (zh) * | 2018-11-20 | 2020-05-26 | 天津市银丰钢绞线股份有限公司 | 一种钢绞线的前处理工艺 |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3355330A (en) * | 1964-03-03 | 1967-11-28 | Hooker Chemical Corp | Metal treating processes |
AT282285B (de) * | 1965-12-22 | 1970-06-25 | Plaut Fa J | Zinkphosphatüberzüge |
FR1469134A (fr) * | 1965-12-28 | 1967-02-10 | Sharples France | Procédé de traitement par phosphatation au manganèse de pièces ayant subi un décapage chimique préalable, et bain permettant de mettre en oeuvre ledit procédé |
US3516875A (en) * | 1966-06-11 | 1970-06-23 | Hooker Chemical Corp | Process for coating ferrous surfaces |
DE1521879B2 (de) * | 1966-07-12 | 1975-08-28 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zum Aufbringen von Phosphatüberzügen auf Eisen und Stahl |
US3432270A (en) * | 1966-07-25 | 1969-03-11 | Amchem Prod | Method for determining nitrite concentration in acidic accelerated phosphating solutions |
DE1911972A1 (de) * | 1969-03-10 | 1970-10-01 | Metallgesellschaft Ag | Verfahren zur Tauchphosphatierung von Eisen und Stahl |
US3617393A (en) * | 1969-10-08 | 1971-11-02 | Dainippon Toryo Kk | Pretreatment before electrophoretic painting |
US3647568A (en) * | 1969-10-28 | 1972-03-07 | Macdermid Inc | Colored phosphate coatings and method of application |
US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
DE2100021A1 (de) * | 1971-01-02 | 1972-09-07 | Collardin Gmbh Gerhard | Verfahren zum Aufbringen von Phos phatschichten auf Stahl, Eisen und Zinkoberflachen |
US3767476A (en) * | 1971-08-31 | 1973-10-23 | Us Army | Method and composition for phosphatizing steel under pressure |
US3758349A (en) * | 1971-09-24 | 1973-09-11 | Oxy Metal Finishing Corp | Method of producing chemical conversion coatings on metal surfaces |
US3850700A (en) * | 1971-10-18 | 1974-11-26 | Amchem Prod | Method and materials for coating metal surfaces |
US3860455A (en) * | 1973-03-16 | 1975-01-14 | Oxy Metal Finishing Corp | Method for phosphatizing ferrous surfaces |
DE2333049C3 (de) * | 1973-06-29 | 1980-09-25 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Phosphatierung von Eisen und Stahl |
US3939014A (en) * | 1974-11-20 | 1976-02-17 | Amchem Products, Inc. | Aqueous zinc phosphating solution and method of rapid coating of steel for deforming |
DE2540684A1 (de) * | 1975-09-12 | 1977-03-17 | Metallgesellschaft Ag | Verfahren zur herstellung von phosphatueberzuegen auf metalloberflaechen |
JPS52141439A (en) * | 1976-04-27 | 1977-11-25 | Nippon Paint Co Ltd | Method of managing chemicallconversion treating liquid for acidic phosphate coating |
DE2736874A1 (de) * | 1977-08-16 | 1979-03-01 | Metallgesellschaft Ag | Verfahren zur erleichterung der kaltumformung von metallen |
DE2907094A1 (de) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | Phosphatierungsloesungen |
JPS5811514B2 (ja) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
GB2080835B (en) * | 1980-07-25 | 1984-08-30 | Pyrene Chemical Services Ltd | Prevention of sludge in phosphating baths |
DE3101866A1 (de) * | 1981-01-22 | 1982-08-26 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metallen |
DE3108484A1 (de) * | 1981-03-06 | 1982-09-23 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur herstellung von phosphatueberzuegen auf metalloberflaechen |
DE3118375A1 (de) * | 1981-05-09 | 1982-11-25 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung |
US4719038A (en) * | 1983-12-27 | 1988-01-12 | Nippon Paint Co., Ltd. | Corrosion resistant, coated metal laminate, its preparation and coating materials |
CA1257527A (fr) * | 1984-12-20 | 1989-07-18 | Thomas W. Tull | Procede de deformation a froid avec enduction lubrifiante amelioree |
US4713121A (en) * | 1985-05-16 | 1987-12-15 | Parker Chemical Company | Alkaline resistant phosphate conversion coatings |
US4596607A (en) * | 1985-07-01 | 1986-06-24 | Ford Motor Company | Alkaline resistant manganese-nickel-zinc phosphate conversion coatings and method of application |
DE3636390A1 (de) * | 1986-10-25 | 1988-04-28 | Metallgesellschaft Ag | Verfahren zur erzeugung von phosphatueberzuegen auf metallen |
US4717431A (en) * | 1987-02-25 | 1988-01-05 | Amchem Products, Inc. | Nickel-free metal phosphating composition and method for use |
-
1989
- 1989-01-24 EP EP89200142A patent/EP0327153B1/fr not_active Expired - Lifetime
- 1989-01-24 ES ES89200142T patent/ES2058464T3/es not_active Expired - Lifetime
- 1989-01-24 DE DE8989200142T patent/DE58905074D1/de not_active Expired - Lifetime
- 1989-02-01 JP JP1020980A patent/JP2713334B2/ja not_active Expired - Lifetime
- 1989-02-01 US US07/305,214 patent/US4950339A/en not_active Expired - Fee Related
- 1989-02-02 CA CA000589900A patent/CA1330515C/fr not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0327153A2 (fr) | 1989-08-09 |
CA1330515C (fr) | 1994-07-05 |
JPH01259180A (ja) | 1989-10-16 |
JP2713334B2 (ja) | 1998-02-16 |
EP0327153A3 (en) | 1990-04-25 |
ES2058464T3 (es) | 1994-11-01 |
DE58905074D1 (de) | 1993-09-09 |
US4950339A (en) | 1990-08-21 |
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