EP0111223B1 - Verfahren zur Phosphatierung von Metalloberflächen sowie hierfür geeignete Badlösungen - Google Patents
Verfahren zur Phosphatierung von Metalloberflächen sowie hierfür geeignete Badlösungen Download PDFInfo
- Publication number
- EP0111223B1 EP0111223B1 EP83111813A EP83111813A EP0111223B1 EP 0111223 B1 EP0111223 B1 EP 0111223B1 EP 83111813 A EP83111813 A EP 83111813A EP 83111813 A EP83111813 A EP 83111813A EP 0111223 B1 EP0111223 B1 EP 0111223B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iron
- content
- baths
- weight
- points
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 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 abstract description 18
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 10
- -1 nickel(II) ions Chemical class 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 4
- 239000008397 galvanized steel Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 description 33
- 229910052725 zinc Inorganic materials 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 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
- 230000009467 reduction Effects 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 2-nitrobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1[N+]([O-])=O ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012360 testing method Methods 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
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- OSKILZSXDKESQH-UHFFFAOYSA-K zinc;iron(2+);phosphate Chemical compound [Fe+2].[Zn+2].[O-]P([O-])([O-])=O OSKILZSXDKESQH-UHFFFAOYSA-K 0.000 description 1
Classifications
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- 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
-
- 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
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
Definitions
- the invention relates to a process for the phosphating of iron, steel and galvanized steel with aqueous, acidic baths which contain zinc phosphate and, if desired, customary activating and / or layering-improving additives.
- the new process is particularly suitable as a pretreatment of the metal surfaces for a subsequent cathodic electrodeposition.
- EP-A-0 056 881 wants to achieve an improvement by working with chlorate-containing zinc phosphate solutions in the temperature range from 30-60 ° C., the 0.5-1.5 g / 1 Zn, 0.4-1, 3 g / I Ni, 10 - 25 g / IP 2 0 5 and 0.8 - 5 g / 1 C10 3 , to which no nitrite is added and in which the weight ratio of Zn: Ni to a value between 1: (0 , 5 - 1.5), Zn: P 2 0 5 to a value between 1: (8 - 85) and free P 2 O 5 : total P 2 0 5 to a value between (0.005 (at approx. 30 ° C) - 0.06 (at approx.
- EP-A-0 036 689 describes a method for applying phosphate coatings on iron, zinc and / or aluminum, which can serve as pretreatment of the metal parts before a cathodic electrodeposition.
- the phosphating solutions disclosed here contain zinc, manganese, phosphate and accelerator, the manganese content being 5 to 33% by weight of the zinc content and a combination of chlorate and nitrobenzenesulfonate being used as the accelerator.
- the content of these solutions in total acid is preferably 20 points and in free acid 0.8 to 1.0 points.
- the application temperature of the solutions is preferably 25 to 50 ° C, in particular 25 to 35 ° C.
- FR-A-23 89 683 also describes a means for applying phosphate coatings on metal surfaces made of iron, zinc or aluminum.
- These phosphating solutions contain zinc ions, phosphate ions.
- Manganese ions - the manganese content being 5 to 50% by weight of the zinc content - an oxidizing agent and boron fluoride.
- the total acid score of the solutions is preferably greater than 20 and the ratio of total acid to free acid is preferably 50: 1 to 100: 1.
- the application temperature of such solutions is equal to or less than 43 ° C. and is preferably in the range from 21 to 43 ° C.
- the metal parts phosphated in this way can also be coated with an electric lacquer.
- the subject of FR-A-13 42 472 is a method for applying phosphate layers on surfaces made of iron, steel, zinc or their alloys by means of solutions which are at least as large as zinc, alkali metal, phosphate, nitrate, nitrate ions of phosphate ions.
- the slight formation of free acid in the solution when metal parts pass through is thus completely compensated for by the addition of nitrite.
- the phosphate coatings formed on the metal surfaces in this way are suitable as a lacquer primer for commercially available lacquers and to facilitate cold working.
- the layer thickness of these phosphate coatings can be increased by adding a small amount of Citric acid and / or tartaric acid or their salts are adjusted or regulated to the phosphating solutions. Such an addition can increase the free acid content in the solutions to 0.4 points.
- the invention is based on the object of proposing acidic, aqueous zinc phosphate-containing baths within the scope of the knowledge known per se for phosphating metal surfaces, which baths work in particular with a significantly lower total acid content.
- the production of high-quality zinc phosphate layers should be ensured, which are characterized in particular by comparatively high iron contents and are accordingly very particularly suitable for subsequent cathodic electrocoating.
- the invention aims to enable a type of process that can be operated effectively at very low temperatures.
- the solution of the task according to the invention is based on the finding that the combination of certain wheel parameters enables the effective reduction in the total acid content and thus the desired reduction in the chemical requirement, but that at the same time these baths at temperatures below 40 ° C effectively contain the desired iron Zinc phosphate layers can be deposited.
- the invention further relates to an aqueous, acidic phosphating bath for the above-mentioned application, the composition of which is also characterized by the features mentioned above and which additionally contains customary activating and / or layer-improving additives.
- the free acid score corresponds to the consumption of ml of n / 10 NaOH in the titration of 10 ml bath solution until the change in the first H 3 P0 4 stage (indicator methyl orange or bromophenol blue).
- the process according to the invention thus uses comparatively high levels of zinc in the bath solution, in particular in comparison with the cited prior art documents, but at the same time only limited amounts of phosphate ions - and ultimately only limited amounts of total acid - are used. It works with baths in which the weight ratio Zn / P0 4 3- is in the range of 1: 2 to 1: 4.
- P0 4 3- content of the bath this means in absolute terms that it is possible to work with comparatively low concentrations of the P0 4 3- value.
- This P0 4 3- content is in the range of 4 to a maximum of 13 g / 1 bath solution. According to the invention, it is particularly expedient to work with a P0 4 3 content in the range of about 4-8 g / 1 bath solution.
- the zinc content in the phosphating bath is in the range of 2-4 g / l bath solution.
- the free acid content is in the range of 0.1 - 0.2 points.
- the pH range for these phosphating baths of the invention is in the range 3.5 - 4.0. This type of bath can be used effectively in the temperature range of 28 - 38 ° C.
- phosphating baths are used, the total acid content of which does not exceed numerically limited values in the range of 15 points. Phosphating baths with a total acid content in the range of 9-15 points are suitable for the process according to the invention.
- auxiliary components or constituents customary in baths of this type can also be used in the phosphating solutions according to the invention. It is of particular importance here, however, that the common use of manganese to this day is not necessary. This is an important advantage of the method according to the invention over other characteristic baths of the prior art, in particular over the so-called low-zinc baths, which operate at a comparatively higher temperature.
- Customary activating additives include components such as chlorate, nitrate, nitrite, hydrogen peroxide, aromatic nitro compounds, simple and / or complex fluorides and / or organic and / or inorganic complexing agents. The following applies here in detail:
- chlorate is generally recommended.
- the chlorate content is expediently in the range from approximately 0.1 to 30 g / l bath solution, preferably in the range from approximately 1.5 to 10 g / l bath solution.
- Any nitrate ions used are expediently in the concentration range of 1 - 10 g / l bath solution. If nitrite ions are to be used in the bathroom, the range of 0.01 - 1 g / 1 bath solution is particularly suitable.
- Hydrogen peroxide can be used in the same area.
- Aromatic nitro compounds, especially 3-nitrobenzenesulfonic acid or its salts, but also other representatives of this class of substances, e.g. B. nitroresorcinol or nitrobenzoic acid are known accelerators in phosphating baths. Compounds of this type are expediently used in amounts of 0.01-2 g / l bath solution.
- the layer formation on the metal surfaces can be improved by adding simple and / or complex fluorides.
- the fluoride ion content is expediently in the range of 0.01-2 g / l bath solution.
- the complex fluoride can be, for example, the SiF 6 2 ion , with concentration ranges of about 0.01-2 g / l bath solution being preferred here too.
- the solutions can also contain complexing agents known per se of organic or inorganic origin.
- Suitable organic complexing agents are, for example, tartaric acid or tartrate, hydroxyethylenediamino-triacetic acid or its salts, gluconic acid or its salts and / or citric acid or its salts.
- Inorganic complexing agents are polyphosphates, for example tripolyphosphate or hexamethaphosphate. Complexing agents of this type are usually present in the bath in quantities of 0.01-5 g / l.
- the treatment bath can contain further metal cations, in particular divalent metal cations.
- the use of nickel (II) in the phosphating bath may be preferred. In the preferred embodiments of the invention, however, the nickel content is limited in relation to the zinc and at most reaches this zinc content. However, the weight ratio Zn / Ni of 1: 0.5 is preferably not exceeded.
- Preferred nickel contents within the framework of the teaching according to the invention can be in the range of approximately 0.01-1 g / 1 bath solution.
- Zinc phosphate layers with a high iron content designed according to the invention are suitable for all types of use of phosphate layers known to date, but they have particular advantages for subsequent cathodic electrocoating. They show a high resistance of the paint film against paint infiltration under corrosive stress as well as high and satisfactory values of the paint adhesion to the metallic surface. The method according to the invention is thus used, for example, in the phosphating of car bodies.
- This concentrate was diluted to a solution with 0.34% Zn, 0.85% P0 4 , 0.34% N0 3 , 0.27% CIO 3 , 0.007% SiF s , 0.007% F and 0.014% 3-nitrobenzenesulfonic acid to give a total acid score of 14.4.
- the free acid was reduced to a pH in the range 3.5-4 by adding sodium hydroxide.
- the dry film thickness of the paint was 18 ⁇ m.
- the parts were then provided with individual cuts and subjected to the salt spray test DIN 50021 for 240 hours.
- the evaluation according to DIN 53167 showed an infiltration of ⁇ 0.1 mm. It follows that the proposed method of working gives a good coating despite the low treatment temperature.
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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)
- Secondary Cells (AREA)
- Glass Compositions (AREA)
- Laminated Bodies (AREA)
- Saccharide Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemically Coating (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83111813T ATE27715T1 (de) | 1982-12-03 | 1983-11-25 | Verfahren zur phosphatierung von metalloberflaechen sowie hierfuer geeignete badloesungen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823244715 DE3244715A1 (de) | 1982-12-03 | 1982-12-03 | Verfahren zur phosphatierung von metalloberflaechen sowie hierfuer geeignete badloesungen |
| DE3244715 | 1982-12-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0111223A1 EP0111223A1 (de) | 1984-06-20 |
| EP0111223B1 true EP0111223B1 (de) | 1987-06-10 |
Family
ID=6179688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83111813A Expired EP0111223B1 (de) | 1982-12-03 | 1983-11-25 | Verfahren zur Phosphatierung von Metalloberflächen sowie hierfür geeignete Badlösungen |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4490185A (ja) |
| EP (1) | EP0111223B1 (ja) |
| JP (1) | JPS59110785A (ja) |
| AT (1) | ATE27715T1 (ja) |
| AU (1) | AU561955B2 (ja) |
| CA (1) | CA1205726A (ja) |
| DE (2) | DE3244715A1 (ja) |
| ES (1) | ES8502168A1 (ja) |
| GR (1) | GR81290B (ja) |
| TR (1) | TR23183A (ja) |
| ZA (1) | ZA839008B (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2484041C1 (ru) * | 2012-02-09 | 2013-06-10 | Юлия Алексеевна Щепочкина | Масса для производства теплоизоляционных плит |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60238486A (ja) * | 1984-05-09 | 1985-11-27 | Nippon Denso Co Ltd | 鉄鋼表面にリン酸塩化成被膜を形成する方法 |
| JPS63270478A (ja) * | 1986-12-09 | 1988-11-08 | Nippon Denso Co Ltd | リン酸塩化成処理方法 |
| US5236565A (en) * | 1987-04-11 | 1993-08-17 | Metallgesellschaft Aktiengesellschaft | Process of phosphating before electroimmersion painting |
| FR2685352A1 (fr) * | 1991-12-24 | 1993-06-25 | Pont A Mousson | Revetement multicouche, avec son procede d'obtention et son application. |
| DE19639597C2 (de) * | 1996-09-26 | 2000-01-20 | Henkel Kgaa | Verfahren zur Phosphatierung von laufenden Bändern aus kalt- oder warmgewalztem Stahl in schnellaufenden Bandanlagen |
| US5900073A (en) * | 1996-12-04 | 1999-05-04 | Henkel Corporation | Sludge reducing zinc phosphating process and composition |
| US6551417B1 (en) | 2000-09-20 | 2003-04-22 | Ge Betz, Inc. | Tri-cation zinc phosphate conversion coating and process of making the same |
| JP4902841B2 (ja) * | 2005-09-14 | 2012-03-21 | 川崎重工業株式会社 | 車体フレーム |
| DE102005047424A1 (de) * | 2005-09-30 | 2007-04-05 | Henkel Kgaa | Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren |
| JP6455524B2 (ja) * | 2014-12-26 | 2019-01-23 | 新日鐵住金株式会社 | 電磁鋼板 |
| EP3828306A1 (de) * | 2019-11-26 | 2021-06-02 | Henkel AG & Co. KGaA | Ressourcenschonendes verfahren zur aktivierung einer metalloberfläche vor einer phosphatierung |
| EP3828307A1 (de) * | 2019-11-26 | 2021-06-02 | Henkel AG & Co. KGaA | Ressourcenschonendes verfahren zur aktivierung einer metalloberfläche vor einer phosphatierung |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA738950A (en) * | 1966-07-19 | Klotzsch Fritz | Process and composition of matter for producing phosphate coatings on metal parts | |
| CA665499A (en) * | 1963-06-25 | I. Maurer James | Cold cleaning and cold phosphate coating process | |
| US3104177A (en) * | 1961-12-12 | 1963-09-17 | Lubrizol Corp | Phosphating process |
| FR1342472A (fr) * | 1962-12-07 | 1963-11-08 | Hoechst Ag | Procédé et agent de phosphatation de surfaces métalliques |
| US3338755A (en) * | 1963-09-03 | 1967-08-29 | Hooker Chemical Corp | Production of phosphate coatings on metals |
| US3619300A (en) * | 1968-11-13 | 1971-11-09 | Amchem Prod | Phosphate conversion coating of aluminum, zinc or iron |
| DE2143957A1 (de) * | 1971-09-02 | 1973-03-08 | Metallgesellschaft Ag | Verfahren zum aufbringen eines phosphatueberzuges auf eisen und stahl |
| FR2389683A1 (en) * | 1977-05-03 | 1978-12-01 | Parker Ste Continentale | Phosphating soln. contg. boron fluoride - for phosphating ferrous and non-ferrous surfaces, e.g. steel, zinc and aluminium |
| GB1591039A (en) * | 1977-05-03 | 1981-06-10 | Pyrene Chemical Services Ltd | Processes and compositions for coating metal surfaces |
| 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 |
| DE2907094A1 (de) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | Phosphatierungsloesungen |
| GB2072225B (en) * | 1980-03-21 | 1983-11-02 | Pyrene Chemical Services Ltd | Process and composition for coating metal surfaces |
| 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 |
| US4498935A (en) * | 1981-07-13 | 1985-02-12 | Parker Chemical Company | Zinc phosphate conversion coating composition |
-
1982
- 1982-12-03 DE DE19823244715 patent/DE3244715A1/de not_active Withdrawn
-
1983
- 1983-11-22 GR GR73035A patent/GR81290B/el unknown
- 1983-11-25 EP EP83111813A patent/EP0111223B1/de not_active Expired
- 1983-11-25 AT AT83111813T patent/ATE27715T1/de not_active IP Right Cessation
- 1983-11-25 DE DE8383111813T patent/DE3371999D1/de not_active Expired
- 1983-11-28 CA CA000442079A patent/CA1205726A/en not_active Expired
- 1983-11-30 TR TR10000/83A patent/TR23183A/xx unknown
- 1983-11-30 US US06/556,746 patent/US4490185A/en not_active Expired - Fee Related
- 1983-12-02 ES ES527732A patent/ES8502168A1/es not_active Expired
- 1983-12-02 ZA ZA839008A patent/ZA839008B/xx unknown
- 1983-12-02 AU AU21920/83A patent/AU561955B2/en not_active Ceased
- 1983-12-03 JP JP58229026A patent/JPS59110785A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2484041C1 (ru) * | 2012-02-09 | 2013-06-10 | Юлия Алексеевна Щепочкина | Масса для производства теплоизоляционных плит |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59110785A (ja) | 1984-06-26 |
| DE3371999D1 (en) | 1987-07-16 |
| CA1205726A (en) | 1986-06-10 |
| EP0111223A1 (de) | 1984-06-20 |
| AU2192083A (en) | 1984-06-07 |
| ES527732A0 (es) | 1984-12-16 |
| US4490185A (en) | 1984-12-25 |
| ES8502168A1 (es) | 1984-12-16 |
| AU561955B2 (en) | 1987-05-21 |
| ATE27715T1 (de) | 1987-06-15 |
| ZA839008B (en) | 1984-07-25 |
| GR81290B (ja) | 1984-12-11 |
| TR23183A (tr) | 1989-06-06 |
| DE3244715A1 (de) | 1984-06-07 |
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