EP1386020A2 - Procede d'application d'un revetement phosphate et utilisation des elements metalliques ainsi phosphates - Google Patents

Procede d'application d'un revetement phosphate et utilisation des elements metalliques ainsi phosphates

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Publication number
EP1386020A2
EP1386020A2 EP02702388A EP02702388A EP1386020A2 EP 1386020 A2 EP1386020 A2 EP 1386020A2 EP 02702388 A EP02702388 A EP 02702388A EP 02702388 A EP02702388 A EP 02702388A EP 1386020 A2 EP1386020 A2 EP 1386020A2
Authority
EP
European Patent Office
Prior art keywords
phosphating solution
phosphate
range
metal parts
phosphating
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.)
Withdrawn
Application number
EP02702388A
Other languages
German (de)
English (en)
Inventor
Thomas Kolberg
Hardy Wietzoreck
Klaus Bittner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
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Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP1386020A2 publication Critical patent/EP1386020A2/fr
Withdrawn legal-status Critical Current

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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
    • C23C22/07—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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations 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
    • C23C22/34—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
    • C23C22/364—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 manganese 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
    • C23C22/73—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 characterised by the process

Definitions

  • the invention relates to a method for applying phosphate coatings on metallic surfaces by wetting with an aqueous phosphating solution, which is used for pre-phosphating, and the use of the metal parts coated according to the invention.
  • Phosphate coatings are widely used as corrosion protection layers, as a forming aid and as a primer for paints and other coatings. Especially if it is used as protection for a limited time, especially during storage and then e.g. are painted, they are referred to as a pre-treatment layer before painting. However, if there is no varnish layer and no other organic coating on the phosphate coating, treatment is used instead of pretreatment. These coatings are also referred to as conversion layers if at least one cation of the metallic surface, that is to say the surface of the metal part, is extracted and also used to build up the layer.
  • Prephosphating has so far been used for galvanized steel strips.
  • Prephosphating is today usually understood to mean a phosphating process in which metallic substrates either without prior cleaning directly after the galvanizing or with a previous cleaning if no galvanizing or storage of oiled substrates, if any, is selected and then phosphated again.
  • Such pre- and post-phosphated are widely used in the automotive industry.
  • no prephosphating processes have been carried out so far known in which work can be carried out largely or completely free of nickel without significant loss of quality.
  • the so-called drying processes are particularly important for the rapid coating of continuously running strips made of at least one metallic material. These strips can be sheets of small or very large width.
  • a phosphate coating by wetting with a phosphating solution is usually applied to these strips directly after the galvanizing, but possibly also after suitable cleaning or degreasing and after rinsing with water or an aqueous medium and after activation of the metallic surface. Rinsing after the phosphate coating has dried could impair it, especially if the phosphate coating is not or only partially crystalline.
  • the substrates coated in this way can be painted.
  • coating processes are used in which phosphate layers are applied to individual parts, wires or strips made of metallic materials, in particular by spraying, spraying, dipping the phosphating solution, which react with cations from the metallic substrates and form a phosphate coating.
  • These substrates are usually rinsed, rinsed if necessary and, if necessary, oiled after drying. Unoiled or oil-free phosphated substrates can be painted.
  • DE-A1-40 13 483 describes a process for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc, manganese, copper, phosphate and oxidizing agents and only traces of nickel, the concentration of Fe 2+ ions being less than 0.1 g / L should be kept. Copper contents in the range from 3 to 5 mg / L are given in the examples.
  • serious problems can occur with the phosphating solutions mentioned there on galvanized surfaces, while the quality of the trication processes based on nickel-rich Zn-Mn-Ni phosphating is achieved.
  • DE-A1-42 10 513 deals with a ' process for producing copper-containing, nickel-free phosphate layers by spraying and / or dipping with a phosphating solution which contains 0.2 to 2 g / L zinc, 5 to 30 g / LP 2 0 5 , 0.005 up to 0.025 g / L copper and 0.5 to 5 g / L of a compound based on hydroxylamine, calculated as HA, through which phosphate crystals with an edge length in the range from 0.5 to 10 ⁇ m are produced.
  • This is said to have low-pore, dense phosphate layers with one low basis weight, excellent corrosion resistance and very good paint adhesion.
  • All copper-containing exemplary embodiments show either a Zn: Mn ratio> 1 or a high nickel content.
  • EP-A-0 675 972 describes a process for producing copper-containing, largely nickel-free zinc phosphate layers with an aqueous composition and the aqueous composition, the 0.026 to 0.074 g / L copper, the 0.45 to 2 g / L zinc, 0.1 up to 10 g / L of compounds based on hydroxylamine, calculated as HA, has total acid values in the range from 5 to 40 points and free acid values in the range from - 0.5 to + 0.8 points and preferably total contents of up to May contain 2 g / L of manganese and cobalt.
  • All copper-containing exemplary embodiments either have a Zn: Mn ratio> 1 or no manganese content at all.
  • DE-A1-196 06 017 suggests a method for phosphating metal surfaces with aqueous, acidic phosphating solutions which have certain contents of zinc, but only traces of manganese and copper in addition to phosphate and at least one accelerator and, if possible, only traces of nickel. No aqueous compositions with a Zn: Mn ratio ⁇ 1 can be used with this method.
  • DE-A1-196 34 685 teaches an aqueous solution for producing phosphate layers and the associated method for phosphating, in which the phosphating solution with zinc, with phosphate, with nitroguanidine as an accelerator and with other additives is adjusted so that phosphate crystallites with a maximum edge length ⁇ 15 ⁇ m should be generated at comparatively low temperatures and that a low layer weight and good paint adhesion should be achieved.
  • All copper-containing exemplary embodiments show a Zn: Mn ratio> 1 or, in the case of a Zn: Mn ratio ⁇ 1, only copper contents up to 0.005 g / L.
  • nitroguanidine is often a disadvantage as an accelerator, because with prolonged use of the phosphating bath - possibly even after a day - in the presence of copper contents, a bath poison is formed that severely affects the formation of layers on steel surfaces: if necessary, the bath must then be drained and new to be set.
  • the object of the invention is to overcome these disadvantages of the prior art and, in particular, to propose a method for applying phosphate coatings on metallic surfaces, in which the subsequent contact with an aqueous liquid or with moisture does not cause any damage and in which the phosphate layer formed at least ' has the same quality as in the prior art.
  • the object is achieved with a method for applying a phosphate coating to metallic surfaces by wetting these surfaces with an aqueous acidic phosphating solution, which is characterized in that the phosphating solution
  • the coating containing polymers, copolymers, crosspolymers, oligomers, silanes and / or siloxanes can be used in addition to water at least one organic film former which contains at least one water-soluble or water-dispersed polymer with an acid number in the range from 5 to 200 and
  • At least one inorganic compound in particle form with an average particle diameter measured on a scanning electron microscope in the range from 0.005 to 0.3 ⁇ m diameter,
  • silane and / or siloxane calculated as silane optionally at least one silane and / or siloxane calculated as silane.
  • the organic film former can be at least one synthetic resin, in particular a synthetic resin based on acrylate, ethylene, polyester, polyurethane, silicone polyester, epoxy, phenol, styrene, urea-formaldehyde, their derivatives, copolymers, cross-polymers, polymers, mixtures or / and copolymers.
  • synthetic resin in particular a synthetic resin based on acrylate, ethylene, polyester, polyurethane, silicone polyester, epoxy, phenol, styrene, urea-formaldehyde, their derivatives, copolymers, cross-polymers, polymers, mixtures or / and copolymers.
  • the organic film former preferably contains synthetic resins and / or polymers or derivatives, copolymers, crosspolymers, polymers, mixtures or / and copolymers based on acrylate, epoxy, phenol, polyethyleneimine, polyurethane, polyvinyl alcohol, polyvinylphenol, polyvinylpyrrolidone and / or polyaspartic acid, in particular Copolymers with a phosphorus-containing vinyl compound.
  • the coating containing silanes / siloxanes can either be deposited from a solution or suspension consisting essentially of silanes or from those which, in addition to silanes, also contain other constituents such as e.g. May contain complex fluoride.
  • those are particularly preferred which contain at least one compound of the type XYZ, ⁇ * ⁇ * z * or / and X * Y * Z * Y * X * , where Y is an organic group having 2 to 50 C atoms .
  • paint includes all types of paint including primers.
  • the polymer-containing coating or the lacquer layer can be applied in one or more layers and in particular the lacquer layer in two, three or four layers.
  • pre-phosphating is used as just defined: as phosphating with a first phosphating solution, in which the pre-phosphated metal parts are subsequently formed, glued to other metal parts, welded to other metal parts and / or post-phosphated with a second phosphating solution and, if necessary, can be painted later.
  • the second phosphating solution can have a similar, slightly different or very different composition and can in principle be applied in a similar or different manner.
  • metal parts includes, in addition to parts such as, for example, metal strip sections, sheets, moldings and uncoated or coated, in particular pre-phosphated, formed and / or painted parts, metal strips.
  • a metal strip can first be pretreated and painted and then cut or first provided with a first pretreatment coating, then cut, then provided with a second pretreatment layer and then painted.
  • a metal strip can first be pretreated and painted and then cut or first provided with a first pretreatment coating, then cut, then provided with a second pretreatment layer and then painted.
  • the processes according to the invention include, on the one hand, strip processes in which strips are coated in a strip system, and, on the other hand, processes for phosphating metallic parts, which according to the invention are e.g. be wetted by spraying, spraying or dipping with a pre- or post-phosphating solution, whereby a phosphate coating is formed; the parts coated in this way are usually rinsed after pre-phosphating (rinse process).
  • a strip can be coated with a first or second phosphating solution in a strip system, the phosphate coating being formed either when the strip is wetted and then the pre-phosphated or also the post-phosphated strip is rinsed (rinse process); or the first or second phosphating solution can be dried on the belt, normally not followed by rinsing (no-rinse process; drying process).
  • the Zn: Mn weight ratio of the first or possibly also the second phosphating solution can vary within wide limits.
  • the zinc: manganese weight ratio of the phosphating solution in the rinse process is preferably kept in the range from 0.05: 1 to 1: 1, particularly preferably in the range from 0.1: 1 to 0.7: 1, very particularly preferably in the range from 0.15: 1 to 0.4: 1, held in the range from 0.05: 1 to 1: 1 in the case of no-rinse processes, particularly preferably in the range from 0.08: 1 to 0.7: 1, very particularly preferably in the range from 0.1: 1 to 0.4: 1.
  • a high content of zinc ions in the first or possibly also in the second phosphating solution promotes, in particular, the avoidance of a free phosphoric acid content in the phosphate layer produced in particular by the drying process and also promotes the crystallinity of the phosphate layer.
  • the zinc ion content in the no-rinse process is preferably 2 to 8 g / L zinc ions, particularly preferably 2.5 to 6 g / L, very particularly preferably 3 to 5 g / L.
  • the zinc ion content is preferably 0.5 to 8 g / L, particularly preferably 1 to 6 g / L.
  • a high content of manganese ions in the first or possibly also in the second phosphating solution promotes in particular the avoidance of a content of free phosphoric acid in the phosphate layer produced - in particular with a drying process - and also promotes the crystallinity of the phosphate layer.
  • the content of manganese ions is preferably 1 to 15 g / L of manganese ions, in the no-rinse process preferably 1.5 to 12 g / L, very particularly preferably 2 to 10 g / L.
  • the manganese ion content is preferably 1.5 to 5.5 g / L, particularly preferably 2 to 4 g / L.
  • a higher content of manganese ions has a positive effect on the quality of the phosphate coating, especially on the paint adhesion and on the corrosion resistance of the subsequently painted metal parts.
  • the content of phosphate ions in the first or possibly also in the second, calculated as P 2 0 5 ⁇ in the rinse process, is preferably 3 to 120 g / L, particularly preferably 3.5 to 80 g / L, very particularly preferably 4th up to 60 g / L, in the no-rinse process preferably 20 to 280 g / L, particularly preferably 40 to 240 g / L, very particularly preferably 80 to 180 g / L.
  • the first and / or the second phosphating solution can in particular be set so that the ratio of the sum of the cations to phosphate ions, calculated as P 2 0 5, is in the range from 1: 0.7 to 1:23. This ratio is preferably in the range from 1: 2 to 1: 27.5 and particularly preferably in the range from 1: 4 to 1: 25.
  • it is advantageous to work with a proportion of free phosphoric acid in the phosphating solution so that a reaction with the metallic surface can take place; this releases metal ions from the metallic surface, which in turn react with the unbound phosphate ions to form insoluble phosphate.
  • the zinc: phosphate weight ratio of the phosphating solution can be kept in the range from 0.002: 1 to 5: 1, with phosphate being calculated as P 2 O s .
  • This ratio is preferably kept in the range from 0.005: 1 to 2: 1, particularly preferably in the range from 0.01: 1 to 0.5: 1.
  • the bath can tend to be instable if the free acid is not increased, and otherwise a greater precipitation of phosphates can occur occur. If this weight ratio is too low, the corrosion resistance and paint adhesion may deteriorate.
  • the first and possibly also the second phosphating solution is free or essentially free of nickel. Even if no nickel is deliberately added to the phosphating solution, a nickel content in the phosphating solution can bath due to the nickel content of the metallic surface of the substrate to be coated, due to the container and piping materials possibly containing nickel and due to trace impurities in the additives from 0.001 to 0.1 g / L, in extreme cases even up to 0.25 g / L due to very nickel-rich metallic surfaces.
  • the first and possibly also the second phosphating solution is free or essentially free of copper.
  • the copper content can range from 0.001 to 4 mg / L.
  • the first or / and second phosphating solution of the process according to the invention is preferably free or essentially free of ions of lead, cadmium, chromium, chloride and / or cyanide, since these substances are not sufficiently environmentally compatible or / and impair the phosphating process and the quality of the phosphate layer can belittle.
  • the amount of the first or optionally also the second phosphating solution which is applied to the metal parts for drying can be very particularly preferably in the range from 1 to 12 ml / m 2 , preferably in the range from 1.5 to 10 ml / m 2 are in the range of 2 to 8 ml / m 2 .
  • a layer with a layer weight - determined on the deposited and dried phosphate layer - can be formed in the range from 0.2 to 5 g / m 2 , preferably in the range from 0.3 to 4 g / m 2 , very particularly preferably at least 0.4 g / m 2 or up to 3 g / m 2 , even more preferably at least 0.5 g / m 2 or up to 2.5 g / m 2 , in particular at least 0.6 or up to 2 g / m 2 .
  • first or possibly second phosphating solution can also contain Fe 2+ ions in the range of up to 5 g / L, in particular in the case of iron surfaces. Neither low nor increased Fe 2+ contents in the phosphating bath normally interfere with a wide variety of metal surfaces.
  • the first or optionally second phosphating solution can have a content of sodium, potassium, calcium or / and ammonium in the range from 0.01 to 20 g / L, preferably a content in the range from 1 to 8 g / L each. L, very particularly preferably in the range from 2.5 to 4 g / L each.
  • the addition of a sodium or ammonium compound is usually advantageous in order to lower the free acid content.
  • the addition of sodium can help to precipitate a portion of the aluminum content in the phosphating solution, which has been brought in, for example, which may impair the layer formation on steel or the paint adhesion, for example as a cryolite.
  • potassium is less recommendable not only because of the somewhat higher costs, but also because of the possibly poorer coating properties.
  • the phosphating solution can have a chloride content in the range from 0.01 to 10 g / L or / and a chlorate content in the range from 0.01 to 5 g / L, preferably chloride in the range from 0. 1 to 6 g / L, preferably chlorate in the range of 0.1 to 3 g / L.
  • chloride and possibly also chlorate or only chlorate in certain quantities should be avoided when phosphating zinc surfaces because of the risk of white spots (specks) if nitrate and / or nitrite are present.
  • the first or / and second phosphating solution can advantageously contain ions of aluminum, boron, iron, hafnium. Molybdenum, silicon, titanium, zirconium, fluoride and / or complex fluoride, at least one water-soluble alkaline earth compound, and / or organic complexing agents such as e.g. Contain citric acid.
  • Fluoride can in particular be present in the range from 0.01 to 5 g / L in free or / and bound form, in particular in the range from 0.02 to 3 g / L, particularly preferably in the range from 0.05 to 2 g / L.
  • the phosphating solution can preferably also contain polymers, copolymers and / or crosspolymers. Such polymers, copolymers and / or cross-polymers can be particularly helpful in the case of phosphate layers which serve as pre-phosphating for forming in order to greatly reduce the so-called “powdering”, namely the rubbing off of the phosphate layer during forming. Particularly preferred are N-containing heterocycles, preferably vinylpyrrolidones.
  • the salary of such polymeric compounds can be 0.05 to 10 g / L in the first or optionally also in the second phosphating solution, preferably 0.1 to 4 g / L.
  • a polymeric alcohol to the first or, if appropriate, also to the second phosphating solution, in order to form phosphoric acid esters with this alcohol, particularly during drying, which have a beneficial effect on lubricants during shaping.
  • the addition of a polymeric alcohol can have an effect on the reaction with the excess free phosphoric acid which may be present in the phosphating solution in order to improve the crystallinity and the water resistance of the phosphate coating.
  • the first and / or the second phosphating solution can contain at least one accelerator.
  • all accelerators can be used. It can have a content of at least one accelerator in the range from 0 to 40 g / L - without a possible (additional) content of at least one compound based on peroxide - preferably in the range from 0.02 to 30 g / L, particularly preferably in the range of 0.1 to 20 g / L.
  • the accelerator can help prevent the formation of hydrogen bubbles on the surfaces. Due to the better contact to the surface to be coated - because it is not partially covered by hydrogen bubbles - more crystal nuclei can be formed there. In the case of zinc surfaces in particular, the presence of an accelerator is not absolutely necessary. However, an accelerator is usually a clear advantage for aluminum, iron and steel surfaces, because it enables the phosphate layer to be made more finely crystalline, because the phosphate layer can be closed more quickly and easily, and because it can improve corrosion protection and paint adhesion.
  • the first and / or the second phosphating solution can advantageously contain a peroxide additive, preferably H 2 O 2 , in a concentration in the range from 1 to 100 g / L, preferably from 5 to 90 g / L, in particular from 10 to 80 g / L, calculated as H 2 0 2 .
  • a peroxide additive preferably H 2 O 2
  • the phosphating solution can have a nitrite content in the range from 0.01 to 0.3 g / L, a nitrate content in the range from 1 to 30 g / L, a content of compounds based on peroxide in the range of 0.001 up to 120 g / L, preferably in the range from 0.01 to 80 g / L and particularly preferably in the range from 1 to 60 g / L, calculated as H 2 0 2 , a content of nitrobenzenesulfonate (NBS), nitropropane, paranitrotoluenesulfonic acid, Nitroethane and / or other nitro organic compounds with oxidizing properties - with the exception of compounds based on nitroguanidine - with a total content in the range from 0.1 to 3 g / L, calculated as N0 2 , a content of compounds based on nitroguanidine in the range 0 , 1 to 6 g / L, a
  • Chlorate additives are usually used in nitrite and nitrate-free baths when zinc surfaces are to be coated.
  • the nitrate content is preferably in the range from 10 to 20 g / L. If working with low nitrate contents or even nitrate-free during prephosphating, an addition of 0.5 to 120 g / L of peroxide, calculated as H 2 O 2 , is preferred.
  • the phosphating solution preferably has a nitrate content in the range from 5 to 25 g / L. Due to the weak effect of this accelerator, higher nitrate levels are often used.
  • the phosphating solution preferably has a content of compounds based on perborate in the range from 0.01 to 5 g / L.
  • the phosphating solution has a content of nitrobenzenesulfonate and / or other nitroorganics with oxidizing properties in the total range from 0.5 to 2 g / L.
  • the phosphating solution preferably has a content of compounds based on hydroxylamine in the range from 0.5 to 4 g / L.
  • the content of compounds based on hydroxylamine, calculated as HA, for the sum of zinc and manganese in the phosphating solution is in the range from 1: 2 to 1: 4.
  • At least one compound based on formic acid, succinic acid, maleic acid, malonic acid, lactic acid, perboric acid, tartaric acid, citric acid or / and a chemically related hydroxycarboxylic acid can be added in order to stabilize the bath or the concentrate or the supplementary solution, in particular for excretions to avoid or reduce from one of these solutions and - in the case of the no-rinse process - to increase the crystallinity of the phosphate layer, which significantly improves the water resistance of the phosphate layer.
  • the total addition of such compounds to such a solution can range from 0.01 to 5 g / L.
  • the content of at least one of these compounds is preferably in the range from 0.1 to 3 g / L.
  • an addition of a polymeric alcohol can also be advantageous in order to form phosphoric acid esters with this alcohol, in particular during drying, phosphoric acid esters, which have a beneficial effect on lubricants during shaping.
  • the addition of a polymeric alcohol can affect the reaction with the excess free phosphoric acid which may be present in the phosphating solution in order to improve the crystallinity and the water resistance of the phosphate coating.
  • the free acid in the coating process according to the invention, a) for rinse processes, can be 0.1 to 10 points, the total acid can be 5 to 50 points total acid can be 3 to 35 points according to Fischer and the ratio of free acid to total acid according to Fischer (S value) can be in the range of 0.01 to 0.9.
  • the free acid in the b) no-rinse process - and each time after diluting 60 g of the treatment bath to 1 liter - the free acid can be 0.1 to 10 points, the total acidity can be 5 to 50 points, the total acidity according to Fischer 3 to 25 points and the ratio of free acid to total acid according to Fischer (S value) can be in the range of 0.01 to 0.9.
  • the values of the free acid are preferably 0.15 to 7 points, the total acid according to Fischer preferably 5 to 30 for the rinse process and 5 to 20 points for the no-rinse process and the ratio of the free acid to the total acid according to Fischer (S- Value), preferably 0.03 to 0J.
  • Values of the free acid in the range from 3 to 5.5 points and values of the total acid according to Fischer are particularly preferred for rinse processes in the range of 10 to 20 points and for no-rinse processes in the range of 8 to 18 points and thus one S value in the range of 0.1 to 0.5.
  • the total content of phosphate ions is determined by titrating the titration solution after addition of 20 ml of 30% neutral potassium oxalate solution against phenolphthalein as an indicator until the change from colorless to red with 0.1 M NaOH after the determination of the free acid.
  • the consumption of 0.1 M NaOH in ml between the envelope with dimethyl yellow and the envelope with phenolphthalein corresponds to total acid according to Fischer (GSF). If this value is multiplied by 0.71, the total content of phosphate ions is obtained (see W. Rausch: "The phosphating of metals". Eugen G. Leuze-Verlag 1988, pp. 300 ff).
  • the so-called S value is obtained by dividing the free acid value by the total acid value according to Fischer.
  • the total acid (GS) is the sum of the divalent cations contained and free and bound phosphoric acids (the latter are phosphates). It is determined by the consumption of 0.1 molar soda layer using the phenolphthalein indicator. This consumption in ml corresponds to the total acid score.
  • the pH of the phosphating solution can be in the range from 1 to 4, preferably in the range from 1.5 to 3.6.
  • the first or second phosphating solution can be applied to the surface of the substrates by knife coating, flooding, spraying, spraying, brushing, dipping, atomizing, rolling, and individual process steps can be combined with one another - in particular spraying and dipping, spraying and squeezing as well as dipping and squeezing, and possibly subsequent squeezing.
  • the first or optionally second phosphating solution can be applied to the metal part by spraying, rolling, flooding and subsequent squeezing, by spraying and subsequent squeezing or by dipping and subsequent squeezing.
  • the technique of application is generally known. In principle, any type of application of the phosphating solution is possible; however, the application variants mentioned are preferred.
  • the squeezing serves to apply a defined volume of liquid per surface of the metal part and can also be replaced by alternative methods; rolling is particularly preferred e.g. with a "chemcoater" or a "roll coater".
  • the second phosphating solution can in principle be applied in any way; their application by spraying, flooding or dipping on the metal part is preferred.
  • the technique of application is generally known.
  • the first or possibly second phosphating solution in the coating can have a temperature in the range from 10 to 80 ° C, in the case of belt drying processes a temperature preferably in the range from 40 to 70 ° C, in the case of belt processes with subsequent rinsing preferably at 40 to 70 ° C and for parts a temperature preferably in the range from 20 to 60 ° C and particularly preferably in the range from 32 to 58 ° C. Only in special cases are the metal parts and / or possibly also the phosphating solution heated to a somewhat elevated temperature, for example in order to accelerate the drying of the applied solution.
  • the liquid film formed on the metal part with the first or optionally second phosphating solution can be dried on the surface of the metal part in the range from 20 and 120 ° C., in particular from 40 ° C., based on PMT temperatures, in particular at 50 to 100 ° C. ,
  • substrates with a metallic surface predominantly containing aluminum, iron, copper, magnesium, tin or zinc can be coated with the phosphating solution, in particular surfaces of at least one of the materials based on aluminum, iron, steel, zinc or / and alloys contains aluminum, iron, copper, magnesium, tin or zinc.
  • the first or second phosphate layer formed in this way can have the following composition: it can be free or essentially free of nickel or have a content of up to 0.5% by weight of Ni and can additionally contain:
  • the nickel content in the phosphate layer also depends on the manganese content of the phosphating solution. It is preferably up to 0.3% by weight, particularly preferably only up to 0.15% by weight.
  • it can contain 6 to 45% by weight of Zn or Mn, preferably 12 to 42% by weight of Zn or Mn, particularly preferably 16 to 38% by weight of Zn or Mn, the layer quality with a higher manganese content usually gets better. It can preferably contain 25 to 60% by weight of phosphate, particularly preferably 28 to 50% by weight, very particularly preferably 30 to 40% by weight.
  • the phosphating solution can be used to deposit a phosphate coating which has a layer weight in the range from 0.2 to 6 g / m 2 , preferably in the range from 1 to 4 g / m 2 .
  • a layer weight of the phosphate layer in the range from 0.2 g / m 2 to 1 g / m 2 is sufficient.
  • a layer weight of up to 6 g / m 2 and thus complete coverage is not disadvantageous if there is no increased consumption of chemicals.
  • an almost complete or complete covering with the phosphate layer is required. This is achieved with a layer weight in the range from 1 g / m 2 to 6 g / m 2 .
  • the coverage of ZnFe alloys can also be relatively incomplete.
  • a layer weight in the range from 0.8 to 2.4 g / m 2 is particularly preferred, in particular from 1 to 2 g / m 2 , especially if the substrates with the prephosphate coating are to be used for welding.
  • the first phosphating layer can be wetted with the second
  • Phosphating solution remain unchanged or slightly dissolved in the upper area and changed in their structure and / or easily removed by the second phosphating solution while from the second Phosphating solution an additional phosphate layer can be deposited, but must not be deposited.
  • the more crystalline the layer the higher the resistance of the first phosphate layer to liquids such as splash water or cleaning liquid, in particular the alkali resistance.
  • the metallic surfaces can be cleaned, pickled, rinsed and / or activated before the first or second phosphating.
  • the cleaning is preferably alkaline and takes place in particular over a period of 2 seconds to 15 minutes, with short times - 2 to 30 seconds - for belt systems.
  • a weak alkaline cleaner can usually be used for metallic surfaces over 2 to 4 minutes outside of the conveyor system. The treatment times are correspondingly shorter for strong alkaline cleaners. It can be advantageous to add a titanium-containing activator to the cleaner. Acid cleaning can also be selected, especially for aluminum and aluminum alloys.
  • the metal parts can be wetted with an activation solution or an activation suspension before wetting with the first and / or with the second phosphating solution.
  • an activation provides the surface with crystal nuclei, which favors the subsequent phosphating and the formation of fine crystalline dense phosphate layers.
  • an aqueous activation solution / suspension with a content of colloidally distributed titanium phosphate can advantageously be selected.
  • any purer water quality is suitable for the subsequent rinsing.
  • Tap water is recommended. If the activation can take place in a separate bath or rinsing step, which is usually advantageous, demineralized water should be used as the solvent after rinsing. With rinse processes, an activation usually has to be carried out. Activation is beneficial for no-rinse processes, but not required. Activation is often very advantageous in order to form crystal nuclei. Activation can be based in particular on titanium. An activation over 10 to 30 seconds is for parts and More than 0.5 to 5 seconds on the tape are often sufficient, even if it can generally take over 0.1 seconds to at least 5 minutes. The activation can also be used for longer than 5 minutes, but is therefore not more effective. It may be advantageous to add copper or / and one of the basically known additives to the activation.
  • a passivation solution directly to the first and / or second phosphate layer, in particular by spraying, dipping or rolling.
  • a rinse solution is preferably used to further increase the corrosion resistance and paint adhesion, the self-assembling containing at least one substance based on Cr, Ti, Zr, Ce or / and other rare earth elements including lanthanum or yttrium, tannin, silane / siloxane, phosphorus can contain molecules, phosphonates or polymers.
  • the phosphated substrates can be rinsed at least once and, if necessary, treated with a rinsing solution for additional passivation after one or between two rinsing processes.
  • a rinsing solution for additional passivation after one or between two rinsing processes.
  • any purer water quality is suitable for rinsing after phosphating.
  • Tap water or demineralized water is recommended - e.g. a dip in cold city water for 10 seconds - and then in the next rinsing step fully demineralized water - e.g. a spray of cold demineralized water for 10 seconds.
  • an additive e.g. zirconium hexafluoride or one of the generally known organic substances can be used, whereby a further improvement in the corrosion resistance and paint adhesion of the coating can be achieved.
  • the pre-phosphating of substrates is advantageous if, for example, the pre-phosphated tape is subsequently formed or if parts are stored, glued and / or welded in the corrosion-protected state.
  • the substrates pretreated in this way can thus be shaped much more easily and are protected against corrosion. It is a particularly advantageous process variant that the metallic surfaces are welded, glued and / or reshaped after pre-phosphating and, if necessary, then phosphated again.
  • the phosphating systems in the automotive industry are equipped with weakly alkaline cleaners, but in some cases also with strongly alkaline cleaners. It was surprising that the first crystalline pre-phosphating layer according to the invention is more resistant to the influence of strong alkaline cleaners in no-rinse processes with an increased cation content. During the short treatment times usually used with a strong alkaline cleaner, the first phosphate layer according to the invention was not, or only slightly, impaired.
  • the metal parts to be coated are first coated according to the invention with a first phosphating solution and then they are wetted, preferably as individual parts or parts connected to one another by joining such as gluing or welding, with a second aqueous, acidic phosphating solution , this second solution is free or substantially free of nickel or up to 8 g / L nickel ions and - 0 to 20 g / L zinc ions, '- 0 to 12 g / L manganese ions,
  • the composition of the second phosphating solution corresponds to a basically known phosphating solution, and the method for applying it is also usually known, although this second solution is generally not dried.
  • the first phosphate layer is preferably applied in a belt system
  • the second phosphate layer can be applied, for example, in an automobile plant or at a device manufacturer.
  • a phosphate layer with the following composition is preferably formed with the second phosphating solution: free or essentially free of nickel or with a content of up to
  • the first or / and second phosphate layer applied to the metal part can be coated with an oil, a dispersion or a suspension, in particular with a forming oil or anti-corrosion oil and / or a lubricant such as a dry lubricant e.g. with a wax-containing mixture.
  • the oil or the lubricant serves as additional temporary protection against corrosion and can also facilitate a forming process, the formed metal part also having increased corrosion resistance.
  • a coating with an oil can also be of interest on the second phosphate layer if the parts to be painted are to be transported to a painting plant further away. After pre-phosphating, oil is preferably applied first before the metallic substrate is deformed.
  • An existing oil layer or lubricant layer can be removed from or from the first or second phosphate layer in order to prepare the coating for painting, forming, assembly, for gluing or for welding.
  • the oil must be removed for subsequent painting while it can be removed in other processes.
  • the metal parts according to the invention which are coated with phosphate can be oiled or degreased and / or cleaned in a so-called belt system if required before they are subsequently phosphated, formed, welded and / or glued before they are coated in a painting system, if necessary.
  • the metal parts provided with a first and possibly also a second phosphate layer can be coated with a lacquer, with a different organic coating or / and are coated with an adhesive layer and, if necessary, then reshaped, the metal parts coated in this way being additionally glued together, mechanically connected and / or welded to other parts.
  • a wide variety of organic coatings are known today or can be used on a phosphate layer. Not all organic coatings fall under the definition of paints. Forming, gluing or welding can also take place in the presence of an oil. The oil is often removed with the cleaner before the second phosphating begins.
  • the metal parts provided with a first or / and second phosphate layer can be provided with a coating either before or only after the shaping or / and assembly.
  • the phosphate-coated metal parts according to the invention can be used for the production e.g. Oiled by equipment cladding if necessary, reshaped if necessary or degreased or / and cleaned if necessary before they are then coated in a painting system if desired. For economic reasons, de-oiling before gluing or welding is preferably avoided.
  • the phosphate-coated metal parts according to the invention can be used for the production e.g. are oiled and reshaped by automobiles, and then several. Metal parts are welded together, glued together or otherwise connected and then the assembled parts can be degreased and / or cleaned before they can then be coated in a paint shop.
  • the metal parts coated by the process according to the invention can be used as pre-phosphated metal parts for a further conversion treatment or for a new conversion pretreatment, in particular before painting, or as pretreated metal parts - especially for the automotive industry - especially before painting or as end-phosphated metal parts, which may still be retrofitted painted, otherwise organic or / and coated with a film, coated with an adhesive layer, formed, assembled and / or welded together.
  • welding is usually a requirement that the phosphate layer is not too thick and that any organic coating that may be present is electrically conductive.
  • the metal parts provided with a first or / and second phosphate layer can be coated with a lacquer, with a different organic coating, with a film or / and with an adhesive layer and, if necessary, formed, the metal parts coated in this way additionally with others Parts glued together, welded together and / or otherwise connected to each other.
  • the phosphate layer produced is less sensitive to aqueous liquids, moisture and other adverse, especially corrosive, media, the more crystalline it is, especially in the case of dried layers.
  • the phosphate layer according to the invention has also proven to be extremely insensitive due to its crystallinity.
  • the crystallinity has surprisingly developed particularly well at higher and high zinc contents in conjunction with a high peroxide content, particularly in the case of drying processes. Even better crystallinity of the phosphate layer and thus an even better water resistance and resistance of this layer against e.g. Alkaline cleaners have resulted if additional activation is carried out before phosphating.
  • a mix of different materials such as Metal parts made of an uncoated steel and pre-phosphated metal parts can be coated at the same time without problems with a method according to the invention.
  • pre-phosphating in cavities can achieve better corrosion protection than in the cited prior art, even without the application of a lacquer.
  • the surface is exceptionally good if after the pre-phosphating and before the painting has been completely or largely nickel-free post-phosphated.
  • Prephosphating layer with regard to corrosion protection, formability,
  • pre-phosphating it is particularly suitable for applying rinse phosphating by spraying and / or dipping at spraying / dipping times in the range from 3 to 15 seconds and at a temperature preferably in the range from 45 to 65 ° C., especially on galvanized surfaces ,
  • the belt speed when drying a pre-phosphating solution on the belt can increase values up to at least 200 m / min if sufficient drying capacity is made available.
  • the fluctuation in the layer weight can be significantly reduced by precisely adjusting the liquid film on the belt and, if necessary, also by avoiding rinsing.
  • Prephosphating is particularly suitable for strip production using the rinse process, in which rinsing is carried out after the phosphate layer has been applied. This process is particularly suitable for automobile production.
  • the coating according to the invention is equivalent in terms of corrosion resistance and paint adhesion to a comparable nickel-rich coating, but is significantly less expensive and significantly more environmentally compatible than the nickel-rich coating. It is particularly surprising that the high-quality coating quality is largely independent of the accelerator or accelerator mixture selected. The coating method according to the invention is also unexpectedly robust. It was also astonishing that the same high quality properties could be achieved over the Zn: Mn ratio in the wide range from 0.5: 1 to 0.3: 1. In addition, the same high-quality properties could also be set outside this range if the composition of the bath was adjusted accordingly.
  • the method according to the invention has the advantage over the previously described and practiced methods that it provides excellent coatings with lower raw material costs and is particularly environmentally friendly. Due to the fact that no nickel is added in this process, fewer heavy metals get into the wastewater, into the phosphate sludge and into the grinding dust. Compared to similar baths, it is possible to lower the bath temperature even further when phosphating.
  • a concentrate for the preparation of the phosphating solution or a supplementary solution for supplementing the phosphating solution can contain zinc, manganese and phosphoric acid in particular, but only sometimes alkalis and / or accelerators.
  • the metal parts coated according to the invention can be used as pre-phosphated metal parts for a further conversion treatment or for a new conversion pretreatment - in particular before painting - or as pretreated metal parts - especially for the automotive industry - especially before painting or as end-phosphated metal parts, which may be subsequently painted , otherwise coated organic, coated with an adhesive layer, formed, assembled and / or welded.
  • BleGh panels made of electrolytically and, in parallel, of hot-dip galvanized or Galvanneal ® coated steel strip were treated as follows:
  • Sheet dimensions 300 x 200 x 0.7 mm.
  • the metal sheets were prepared for the application of the phosphating solution according to the invention by immersing them in an activation solution containing titanium phosphate and then squeezing off the liquid film.
  • RB rinse belt process
  • RT partial rinse process
  • NR no-rinse belt process.
  • Table 1 Composition of the pre-phosphating solutions in g / L or points of free acid (FS) or total acid according to Fischer (GSF).
  • the free acid in the no-rinse method 60 g of the concentrate were taken, made up to 1 l with deionized water and then for the . Free acid titration used. In the case of the rinse process, the free acid was adjusted by adding NaOH or Na 2 CO 3 .
  • the pre-phosphated test panels were coated immediately afterwards either with only a cathodic automotive dip paint or with an overall automotive paint structure and gave the usual automotive paint tests, e.g. Cross-cut testing after wet storage, VDA climate alternating test, etc., sometimes just as good with nickel-free coatings as with the test panels, which were phosphated twice according to the invention and then painted (Table 3).
  • the pre-phosphated sheets made of electrolytically galvanized (EG) or hot-dip galvanized steel (HDG) and hot-dip galvanized steel with a coating based on ZnFe (Galvanneal ® ) were subjected to various forming tests.
  • EG electrolytically galvanized
  • HDG hot-dip galvanized steel
  • ZnFe ZnFe
  • a forming oil Quaker ® N6130 typically used in the automotive industry was applied in an amount of approx. 0.5 g / m 2 to all pre-phosphated and non-pre-phosphated test sheets
  • Test series B was carried out on electrolytically galvanized steel strips or on hot-dip galvanized or Galvanneal ® coated steel sheets.
  • the pre-phosphating layer had excellent crystallinity and resistance to water and other liquids in the no-rinse processes, so that no staining occurred, for example due to splash water which wetted the phosphate layer, absorbed soluble components and then dried.
  • the pre-phosphated or non-pre-phosphated tapes were then cut if necessary; all belt sections were then mildly alkaline cleaned, rinsed and treated with a titanium-containing activation solution.
  • Table 2 Compositions of post-phosphating solutions 1 and 2 with content in g / L and acidity in points:
  • Table 3 Results of the adhesion and corrosion tests on galvanized surfaces during the 1st cross-cut test according to DIN / EN ISO 2409 after storage for 40 h in 5% NaCI solution (BMW specification),
  • B 1 to VB 7 relate to test series A.
  • B 7 to VB 13 relate to test series B, in which additional phosphating was carried out.
  • test results of test series A already show excellent paint adhesion and corrosion resistance even without post-phosphating.
  • the results are so good in some cases that the good results cannot be improved or can only be improved slightly by additional post-phosphating, as the comparison with the test results of test series B, in which post-phosphating solution 1 or 2 was post-phosphating, indicates.
  • post-phosphating solution 1 or 2 was post-phosphating

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Abstract

L'invention concerne un procédé d'application d'un revêtement phosphate sur des surfaces métalliques par mouillage de ces surfaces avec une solution de phosphatation acide aqueuse. Ledit procédé est caractérisé en ce que la solution de phosphatation contient 0,2 à moins de 10 g/L d'ions zinc, 0,5 à 25 g/L d'ions manganèse, et 2 à 300 g/L d'ions phosphate, calculé en tant que P2O5, et en ce que la solution de phosphatation n'est pas pourvue de cuivre, ni de nickel. Selon ledit procédé, les éléments métalliques ainsi pré-phosphatés sont ensuite formés, collés à d'autres éléments métalliques, soudés à d'autres éléments métalliques et/ou phosphatés à nouveau, et éventuellement revêtus ultérieurement d'au moins un revêtement contenant un polymère ou d'au moins au moins une couche de vernis.
EP02702388A 2001-03-06 2002-03-02 Procede d'application d'un revetement phosphate et utilisation des elements metalliques ainsi phosphates Withdrawn EP1386020A2 (fr)

Applications Claiming Priority (3)

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DE10110833A DE10110833B4 (de) 2001-03-06 2001-03-06 Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
DE10110833 2001-03-06
PCT/EP2002/002270 WO2002070781A2 (fr) 2001-03-06 2002-03-02 Procede d'application d'un revetement phosphate et utilisation des elements metalliques ainsi phosphates

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WO2002070781A3 (fr) 2003-11-13
DE10110833A1 (de) 2002-09-19
DE10110833B4 (de) 2005-03-24
US20040065389A1 (en) 2004-04-08
JP2005501173A (ja) 2005-01-13
CA2440127A1 (fr) 2002-09-12
WO2002070781A2 (fr) 2002-09-12

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