EP0461133A1 - Process for producing zinc/barium phosphate coatings on metal surfaces. - Google Patents
Process for producing zinc/barium phosphate coatings on metal surfaces.Info
- Publication number
- EP0461133A1 EP0461133A1 EP90903372A EP90903372A EP0461133A1 EP 0461133 A1 EP0461133 A1 EP 0461133A1 EP 90903372 A EP90903372 A EP 90903372A EP 90903372 A EP90903372 A EP 90903372A EP 0461133 A1 EP0461133 A1 EP 0461133A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- zinc
- phosphate
- barium
- nitrite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C23C22/367—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 alkaline earth metal 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
- C23C22/22—Orthophosphates containing alkaline earth metal cations
Definitions
- the invention relates to a method for producing phosphate coatings on metal surfaces, in particular surfaces made of iron, steel, zinc, zinc / nickel alloys and / or aluminum and their alloys by means of an acidic aqueous solution containing zinc (II) ions, Barium (II) ions, phosphate ions and accelerators and, if appropriate, other additives, and the use of this process to prepare the surfaces for subsequent painting, in particular cathodic electrocoating.
- layer-forming phosphating treatment with acidic phosphating solutions, which typically contain phosphoric acid, oxidizing compounds and divalent layer-forming ions such as zinc alone or together with calcium, manganese, iron, cobalt, nickel and other metal ions, results in amorphous or crystalline phosphate layers on metal surfaces generated.
- acidic phosphating solutions typically contain phosphoric acid, oxidizing compounds and divalent layer-forming ions such as zinc alone or together with calcium, manganese, iron, cobalt, nickel and other metal ions, results in amorphous or crystalline phosphate layers on metal surfaces generated.
- phosphophyllite Zn2Fe (PO_ ⁇ ) 2 is formed as crystalline phosphate phases.
- H2 ⁇ and / or Hopeit Zn3 (P ⁇ 4) 2-4H2 ⁇ or isostructural phases doped with other divalent metal ions and, in the presence of calcium, also scholzite Zn2Ca (P ⁇ 4) 2-2H2 ⁇ (WA Roland, K.-H.
- the object of the present invention was to provide a method for producing phosphate coatings on metal surfaces, wherein conversion layers are produced which have a particularly high alkali resistance and are exposed to thermal stresses due to the baking temperatures typically used for cathodic electrocoating and higher temperatures are not subject to changes.
- acidic aqueous phosphating solutions which essentially contain barium (II), zinc (II) and phosphate ions can produce conversion layers on metal surfaces which have a high level Have alkali resistance and are not subject to changes under thermal loads of up to around 300 ° C.
- the present invention thus relates to a method for producing phosphate coatings on surfaces of iron, steel, zinc, galvanized steel, nickel, aluminum and / or their alloys or aluminum-steel composites by spraying, splash-dipping and / or dipping with an aqueous Solution containing: 0.01 to 5 g / 1 zinc (II) ions, 0.3 to 10 g / 1 barium (II) ions, 3 to 50 g / 1 phosphate ions, 0 to 2 g / 1 fluoride -Ions and as accelerators: 0.5 to 30 g / 1 nitrate ions and / or 0.01 to 1 g / 1 nitrite ions and / or 0.2 to 10 g / 1 chlorate ions and / or 0, 1 to 2 g / 1 of an organic nitro compound and / or 0.01 to 5 g / 1 of a peroxo compound, the pH of the solution being adjusted between 2 and 4.
- an aqueous Solution
- aqueous solutions which contain 0.5 to 1.5 g / 1 zinc (II) ions, 0.3 to 1.5 g / 1 barium (II) ions,
- the treatment temperature is, depending on the type of application, between 40 and 80 ° C. Depending on the type of application, the treatment times are between 1 and 10 minutes. In this way, crystalline, dense and homogeneous coatings with layer weights of approximately 0.5 to approximately 10 g / m2 are produced.
- the aluminum materials to be treated by the method according to the invention include the pure metal and its alloys. Pure aluminum, AlMg, AlCu and AlMgSi alloys are therefore mentioned as examples. A detailed description of these materials can be found, for example, in the "Aluminum Pocket Book", 14th edition, Aluminum-Verlag, Düsseldorf, 1983.
- the steels (CRS) to be treated with the aid of the method according to the invention are, in particular, consumer goods such as automobile bodies, automobile accessories and spare parts, agricultural equipment, refrigerators and other types of small parts which are usually used in the form of sheet metal.
- the term "galvanized steel” includes galvanizing by electrodeposition (ZE) and hot dip application (Z) and thus refers to zinc and known zinc alloys, in particular zinc / nickel alloys.
- the aqueous phosphating solutions can be applied to the substrate surfaces both by spraying, by immersion and by spray-immersion.
- the spraying time must be selected in such a way that that a largely closed phosphate layer is formed.
- Modern full immersion systems are characterized by a large number of steps connected in series. The term "full immersion system" results from the phosphating by immersion application. In other process steps, spraying processes are also carried out, with spraying out of the immersion bath after the body has appeared.
- a separate activation step may be important for optimal phosphating.
- pre-cleaning and activation of the layer to be phosphated it is usually cleaned, rinsed and then activated before phosphating in several work steps.
- aqueous suspensions containing titanium phosphate according to the prior art can be used here.
- the phosphate layers obtained can also be aftertreated in a manner known per se, i.e. passivated.
- Compliance with the concentration ranges of the aqueous phosphating baths according to the invention is an essential component for the production of high quality, i.e. uniform phosphate coatings. If the concentrations are undershot, the layers become uneven. In particular, their suitability for subsequent electrodeposition painting decreases.
- a certain proportion of the zinc can be replaced by cobalt and / or magnesium in the barium-dizinc phosphates obtained according to the invention.
- a further preferred embodiment of the present invention is that aqueous solutions are used which additionally contain 0.01 to 0.6 g / l of cobalt (II) ions.
- a further preferred embodiment of the present invention consists in using aqueous solutions which additionally contain 0.01 to 0.3 g / 1 magnesium (I ⁇ ) ions included. Diadoch replacement of zinc ions also enables the simultaneous use of cobalt (II) ions and magnesium (II) ions.
- the aqueous solutions used for the process according to the invention can furthermore also contain 0.01 to 0.5 g / 1 iron (III) ions.
- the phosphating layers produced when the process according to the invention is carried out prove to be very resistant to attack by alkalis, i.e. in a strongly alkaline environment, as well as against thermal loads.
- Another advantage of the process according to the invention is that the sludge formation in the phosphating bath is extremely low, especially if the preferred procedures are followed.
- the method according to the invention can advantageously be used for the pretreatment of metal surfaces before subsequent painting; it is used in particular for the pretreatment of metal surfaces before cathodic electrocoating.
- the phosphating baths for carrying out the process according to the invention are generally prepared in the customary manner which is known per se to the person skilled in the art.
- the starting materials for the production of the phosphating bath can be, for example, the oxides, nitrates or carbonates of the required metal cations, for example barium carbonate or nitrate and zinc nitrate or oxide.
- Cobalt and magnesium are preferably used in the form of cobalt nitrate and magnesium oxide, iron in the form of iron nitrate.
- the nitrate required is preferably introduced as a zinc and / or barium salt, as mentioned above, if appropriate also in Form of the sodium salt.
- nitrite, chlorate and fluoride ions are also added to the bath in the form of the sodium salts; the fluoride ions optionally also in the form of fluorosilicic acid and / or fluoroboric acid.
- the sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic nitro compound, and hydrogen peroxide is used as the preferred peroxo compound.
- Phosphoric acid serves as the source of the phosphate ions.
- the pH of the bath is adjusted to the desired value by adding aqueous sodium hydroxide solution.
- the process is carried out in the usual process sequence (see Table 1) with the stages: mechanical and chemical cleaning and degreasing, rinsing, pickling, rinsing, optionally activating, phosphating, VE rinsing.
- the phosphate layers produced were finely crystalline and closed; they consisted exclusively of barium dizinc phosphate.
- phosphated sheets were coated with a cathodic electro-dip coating (Aqualux R K from ICI, Germany, based on epoxy resin) and dried at 180 ° C. for 20 minutes. The dry film thickness was 20 ⁇ m. The Ba / Zn phosphate layer was not changed in this treatment.
- the sheets were then provided with a single cut in accordance with DIN 53 167 and subjected to the salt spray test in accordance with DIN 50 021 for a period of 480 h. The evaluation was carried out according to DIN 53 167.
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Un procédé permet de revêtir avec du phosphate des surfaces métalliques, notamment en fer, acier, zinc, alliages de zinc/nickel, aluminium et/ou ses alliages ou en matériaux composites d'aluminium et d'acier, par pulvérisation, pulvérisation et immersion et/ou immersion, avec une solution aqueuse contenant entre 0,01 et 5 g/l d'ions de zinc(II), entre 0,3 et 10 g/l d'ions de barium(II), entre 3 et 50 g/l d'ions de phosphate, entre 0 et 2 g/l d'ions de fluorure, et en tant qu'accélérateurs, entre 0,5 et 30 g/l d'ions de nitrite et/ou entre 0,01 et 1 g/l d'ions de nitrite et/ou entre 0,2 et 10 g/l d'ions de chlorate et/ou entre 0,1 et 2 g/l d'un composé nitro-organique et/ou entre 0,01 et 5 g/l d'un composé peroxyde. Le pH de la solution est ajusté pour se situer entre 2 et 4.A process makes it possible to coat with phosphate metal surfaces, in particular iron, steel, zinc, zinc / nickel alloys, aluminum and / or its alloys or aluminum and steel composite materials, by spraying, spraying and immersion and / or immersion, with an aqueous solution containing between 0.01 and 5 g / l of zinc (II) ions, between 0.3 and 10 g / l of barium (II) ions, between 3 and 50 g / l of phosphate ions, between 0 and 2 g / l of fluoride ions, and as accelerators, between 0.5 and 30 g / l of nitrite ions and / or between 0.01 and 1 g / l of nitrite ions and / or between 0.2 and 10 g / l of chlorate ions and / or between 0.1 and 2 g / l of a nitro-organic compound and / or between 0.01 and 5 g / l of a peroxide compound. The pH of the solution is adjusted to be between 2 and 4.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3906898 | 1989-03-03 | ||
DE3906898A DE3906898A1 (en) | 1989-03-03 | 1989-03-03 | ZINC-BARIUM PHOSPHATION OF METAL SURFACES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0461133A1 true EP0461133A1 (en) | 1991-12-18 |
EP0461133B1 EP0461133B1 (en) | 1994-01-26 |
Family
ID=6375498
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90903372A Expired - Lifetime EP0461133B1 (en) | 1989-03-03 | 1990-02-21 | Process for producing zinc/barium phosphate coatings on metal surfaces |
EP90103326A Withdrawn EP0385251A1 (en) | 1989-03-03 | 1990-02-21 | Zinc-barium phosphating of metal surfaces |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90103326A Withdrawn EP0385251A1 (en) | 1989-03-03 | 1990-02-21 | Zinc-barium phosphating of metal surfaces |
Country Status (6)
Country | Link |
---|---|
EP (2) | EP0461133B1 (en) |
KR (1) | KR920700308A (en) |
AU (1) | AU5109490A (en) |
DE (2) | DE3906898A1 (en) |
PT (1) | PT93307A (en) |
WO (1) | WO1990010094A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3139795B2 (en) * | 1991-10-29 | 2001-03-05 | 日本パーカライジング株式会社 | Metal surface treatment agent for composite film formation |
JP3417653B2 (en) * | 1994-05-11 | 2003-06-16 | 日本パーカライジング株式会社 | Pretreatment method for painting aluminum material |
KR100317680B1 (en) * | 1999-04-29 | 2001-12-22 | 이계안 | Surface treatment agent for treating aluminium alloy and steel plate simultaneously before painting |
DE10261014B4 (en) * | 2002-12-24 | 2005-09-08 | Chemetall Gmbh | Process for coating metal surfaces with an alkali phosphating solution, aqueous concentrate and use of the metal surfaces coated in this way |
EP4121580A1 (en) * | 2020-03-19 | 2023-01-25 | ThyssenKrupp Steel Europe AG | Method for generating a phosphate conversion coating and nickel-free phosphating solution |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3090709A (en) * | 1953-08-10 | 1963-05-21 | Lubrizol Corp | Phosphate coating of metals |
FR1300295A (en) * | 1961-06-22 | 1962-08-03 | Parker Ste Continentale | Phosphating process for rubbing metal surfaces |
DE1184589B (en) * | 1961-06-24 | 1964-12-31 | Metallgesellschaft Ag | Process and means for applying finely crystalline phosphate layers to metal surfaces |
US3104177A (en) * | 1961-12-12 | 1963-09-17 | Lubrizol Corp | Phosphating process |
FR2001032A1 (en) * | 1968-01-31 | 1969-09-19 | Nippon Kokan Kk | |
JPS4824135B1 (en) * | 1968-12-20 | 1973-07-19 | ||
US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
-
1989
- 1989-03-03 DE DE3906898A patent/DE3906898A1/en not_active Withdrawn
-
1990
- 1990-02-21 WO PCT/EP1990/000287 patent/WO1990010094A1/en active IP Right Grant
- 1990-02-21 DE DE90903372T patent/DE59004443D1/en not_active Expired - Fee Related
- 1990-02-21 EP EP90903372A patent/EP0461133B1/en not_active Expired - Lifetime
- 1990-02-21 KR KR1019900702376A patent/KR920700308A/en not_active Application Discontinuation
- 1990-02-21 EP EP90103326A patent/EP0385251A1/en not_active Withdrawn
- 1990-02-21 AU AU51094/90A patent/AU5109490A/en not_active Abandoned
- 1990-03-01 PT PT93307A patent/PT93307A/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9010094A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP0385251A1 (en) | 1990-09-05 |
KR920700308A (en) | 1992-02-19 |
DE59004443D1 (en) | 1994-03-10 |
AU5109490A (en) | 1990-09-26 |
EP0461133B1 (en) | 1994-01-26 |
WO1990010094A1 (en) | 1990-09-07 |
DE3906898A1 (en) | 1990-09-06 |
PT93307A (en) | 1990-11-07 |
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