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EP1090160B1 - Commande de poids de couche lors de la phosphatation d'une bande - Google Patents

Commande de poids de couche lors de la phosphatation d'une bande Download PDF

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Publication number
EP1090160B1
EP1090160B1 EP99937820A EP99937820A EP1090160B1 EP 1090160 B1 EP1090160 B1 EP 1090160B1 EP 99937820 A EP99937820 A EP 99937820A EP 99937820 A EP99937820 A EP 99937820A EP 1090160 B1 EP1090160 B1 EP 1090160B1
Authority
EP
European Patent Office
Prior art keywords
phosphating
ions
range
phosphating solution
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99937820A
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German (de)
English (en)
Other versions
EP1090160A1 (fr
Inventor
Jörg Riesop
Franz-Gerd Ricke
Frank Panter
Dieter Geruhn
Hubertus Peters
Manfred Wessel
Andreas Klare
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.)
Henkel AG and Co KGaA
ThyssenKrupp Steel Europe AG
Original Assignee
Henkel AG and Co KGaA
ThyssenKrupp Stahl AG
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Publication of EP1090160A1 publication Critical patent/EP1090160A1/fr
Application granted granted Critical
Publication of EP1090160B1 publication Critical patent/EP1090160B1/fr
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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
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
    • 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
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • 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
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium 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
    • C23C22/77—Controlling or regulating of the coating process

Definitions

  • the invention relates to a method for controlling the layer weight in the phosphating of steel strip galvanized on one or both sides.
  • the layer weights can be kept reliably in the desired range of about 1 to about 2 g / m 2 even when the belt speed and thus the phosphating time or the change in other phosphating parameters are changed.
  • layer weight is common in the field of phosphating metal surfaces.
  • layer weight or more detailed “phosphate layer weight”
  • area-related mass is also used. This is understood to mean the mass, based on a unit area, of the metal phosphate layer produced on the metal surface by the phosphating. It is usually given in g / m 2 . It can be determined by weighing a phosphated metal sheet with a known surface, detaching the metal phosphate layer and weighing the metal sheet again. The mass of the metal phosphate layer based on an m 2 can be calculated from the determined weight difference, taking into account the surface of the metal sheet. A 0.5% by weight chromic acid solution can be used, for example, to detach the metal phosphate layer. The method of determining the layer weight is described in more detail in the German standard DIN 50942.
  • the layer weight represents an essential parameter for checking the phosphating result. Depending on the intended use of the phosphated metal parts, layer weights are sought in different areas.
  • the present invention is preferably concerned with sheet metal used in automotive engineering. Layer weights of above 0.8 g / m 2 , but at most about 4 g / m 2, are aimed for.
  • the layer weights should preferably be below 3 g / m 2 and in particular be about 1 to about 2 g / m 2 .
  • phosphating metal strips in particular electrolytically galvanized or hot-dip galvanized steel strips are state of the art known.
  • WO 91/02829 describes a method for Phosphating of electrolytically and / or hot-dip galvanized steel strip through short-term treatment with acid phosphating solutions, which in addition to zinc and Phosphate ions Manganese and nickel cations as well as anions containing oxygen Contain acids with accelerator effect. Under the latter term are especially to understand nitrate ions.
  • DE-A-35 37 108 also describes a process for the phosphating of electrolytically galvanized steel strips Treatment with acid phosphating solutions, which in addition to zinc, manganese and Phosphate ions other metal cations such as nickel ions and / or Anions of oxygen-containing acids with accelerating action, in particular Nitrate ions.
  • acid phosphating solutions which in addition to zinc, manganese and Phosphate ions other metal cations such as nickel ions and / or Anions of oxygen-containing acids with accelerating action, in particular Nitrate ions.
  • the content of zinc cations lies in that relatively deep range from 0.1 to 0.8 g / l.
  • German patent application DE-A-196 39 596 tries to provide a phosphating process which, on the one hand, solves the problem of speck formation and, on the other hand, makes it possible to also use galvanized steel strips or the non-galvanized side of one-side galvanized steel strips with the short phosphating times customary in strip systems with a to provide a closed crystalline phosphate layer.
  • "Specks” are understood to be whitish corrosion spots on the metal surface that show a crater-like appearance in microscopic images. Such specks often occur on galvanized steel surfaces if the phosphating solution has too high levels of chloride ions and / or nitrate ions.
  • this object is achieved by a method for phosphating steel strip or steel strip galvanized on one or both sides or alloy galvanized by spraying or dipping treatment for a period of time in the range from 2 to 15 seconds with an acidic, zinc and manganese-containing phosphating solution at a temperature in the range from 40 to 70 ° C, characterized in that the phosphating solution 1 to 4 g / l Zinc ions, 0.8 to 3.5 g / l manganese ions 10 to 30 g / l phosphate ions 0.1 to 3 g / l Hydroxylamine in free, ionic or bound form and contains no more than 1 g / l nitrate ions, has a free acid content in the range of 0.4 to 4 points and a total acid content in the range of 12 to 50 points.
  • DE-A-197 40 953 describes a method for phosphating steel strip or steel strip galvanized on one or both sides or galvanized with alloys by spraying or dipping treatment for a period of time in the range from 2 to 20 seconds with an acid, zinc, magnesium and manganese-containing phosphating solution with a temperature in the range from 50 to 70 ° C, characterized in that the phosphating solution is free of nitrate ions and that it 1 to 4 g / l Zinc ions, 1.2 to 4 g / l manganese ions 1 to 4 g / l magnesium ions 10 to 30 g / l phosphate ions 0.1 to 3 g / l Hydroxylamine in free, ionic or bound form contains, has a free acid content in the range of 0.4 to 4 points and a total acid content in the range of 15 to 45 points.
  • free acid and total acid are in the field of Commonly known phosphating. They are determined by looking at the acidic one Titrate the bath sample with 0.1 normal sodium hydroxide solution and measure its consumption. The Consumption in ml is given as a score. In this document, under the Score of free acid consumption in ml of 0.1 normal sodium hydroxide solution understood to 10 ml bath solution, diluted to 50 ml with deionized water was to titrate to a pH of 4.0. Similarly, the score gives the Total acid consumption in ml up to a pH of 8.2.
  • the layer weight to adjust to the desired range. For example, with otherwise same bath parameters by changing the belt speed. Usually, however, a certain belt speed is specified, so that the phosphating bath parameters must be set so that they predetermined belt speed layer weights in the desired range result.
  • the belt speeds can fluctuate considerably for example in the range between about 20 and about 180 m / min.
  • options for regulating the layer weight are known: Change in the temperature of the phosphating bath, change in the free acid, the total acidity and / or the concentration of the layer-forming ions. This However, changes only respond very slowly, so it takes considerable time takes until layer weights are obtained in the desired range. It is particularly problematic, the layer weight by changing the Adjust bath composition. These changes are often only with one undo considerable time delay. At least they are with an additional consumption of phosphating chemicals and thus with additional costs.
  • EP-A-0 111 246 relates to a process for phosphating electrolytically galvanized steel strips with acid phosphating solutions which, in addition to zinc and phosphate ions, contain further metal cations, for example nickel and iron (II), and accelerators such as nitrate.
  • the zinc (II) cation content is 1 to 2.5 g / l, the free acid content 0.8 to 3 points and the total acid / free acid weight ratio 5 to 10.
  • the duration of the treatment should not be significantly longer than 5 sec.
  • the phosphating solution contains 0.4 g / l nickel (II) and 3 mg / l iron (II) ions. Layer weights below 2 g / m 2 and a constant quality of the phosphate coating are achieved.
  • WO-A-95/07370 describes a nickel-free phosphating process with phosphating solutions, the 0.3 to 2 g / l zinc (II), 0.3 to 4 g / l manganese (II), 5 to 40 g / l phosphate ions, 0.1 up to 5 g / l hydroxylamine and / or 0.2 to 2 g / l m-nitrobenzenesulfonate and at most 0.5 g / l Contain nitrate ions, the manganese content being at least 50% of the zinc content is.
  • EP-A-0 315 059 relates to a phosphating solution which uses hydroxylamine as an accelerator contains to form Zn / Fe phosphate layers of certain crystal structure. These solutions preferably contain 0.02 to 0.2% by weight of zinc, 0.05 to 5.0% by weight Hydroxylamine and 0.001 to 0.5% by weight of iron (II).
  • the present invention relates to a method for controlling the layer weight in the phosphating of steel strip galvanized on one or both sides with a phosphating solution which contains 1 to 6 g / l zinc ions and 10 to 30 g / l phosphate ions and contains a content of Fe (II) ions in the range from 3 to 100 mg / l, characterized in that between 3 and 20 mg / l Fe (II) ions are added to the phosphating solution to reduce the layer weight by 0.1 g / m 2, or in that Phosphate solution to increase the layer weight by 0.1 g / m 2 between 3 and 20 mg / l Fe (II) ions by oxidation to Fe (III) ions.
  • a phosphating solution which contains 1 to 6 g / l zinc ions and 10 to 30 g / l phosphate ions and contains a content of Fe (II) ions in the range from 3 to 100 mg / l, characterized in that
  • This process is based on the surprising observation that, with the process parameters remaining the same, the more iron (II) ions the phosphating bath contains, the lower the layer weight. It was observed that, in the case of layer weights in the introductory range, with otherwise the same phosphating parameters, the layer weight is reduced by 0.1 g / m 2 when the phosphating bath is between 3 and 20 mg / l, in particular about 5 to about 10 mg / l Iron (II) ions added. The longer the treatment time, the less iron (II) is sufficient.
  • the preferred procedure is to prepare a stock solution of a soluble iron (II) salt with a known iron concentration and add it to the phosphating bath if necessary.
  • the soluble iron (II) salts used are preferably salts of anions which do not have a negative effect on the phosphating result and corrosion protection. Iron (II) sulfate is particularly suitable for this.
  • the process according to the invention therefore makes it possible to counteract the increase in the layer weight while reducing the belt speed by increasing the concentration of iron (II) ions in the phosphating bath by 3 to about 20 mg / l, depending on the treatment time, in order to reduce the Layer weight to achieve 0.1 g / m 2 .
  • iron (II) ions are in the range from 3 to 100 mg / l, preferably between about 10 and about 100 mg / l and in particular between about 15 and about 55 mg / l
  • belt speeds in the range from about 20 to 1 are obtained about 180 m / min and resulting phosphating times of about 2 to about 15 seconds, reliable layer weights in the range between about 1 and about 2 g / m 2 .
  • the process weight is to be counteracted when the process parameters are changed again, for example an increase in the belt speed and a reduction in the phosphating time, the corresponding amount of iron (II) ions must be removed from the phosphating bath.
  • the corresponding amount of iron (II) ions must be removed from the phosphating bath.
  • the easiest way to do this is to add the calculated amount of an oxidizing agent to the phosphating bath in order to oxidize the desired amount of iron (II) ions to iron (III) ions.
  • the process according to the invention is preferably operated in such a way that the Phosphating solution supplemented with supplementary solutions that do not contain iron (II).
  • This has the consequence that the Iron (II) content of the phosphating bath decreased over time, so that the Increase layer weights over time. This effect can be desirable as long as the layer weight is in the technically preferred range. An unwanted one further increase can then be counteracted by that Phosphating bath adds the appropriate amount of iron (II) ions.
  • Phosphating solutions commonly used which in addition to zinc ions also ions of one or contain several other divalent metals.
  • Phosphating baths commonly used which additionally include one or more of the following Cations contain: 1 to 5 g / l manganese ions, 1 to 4 g / l magnesium ions, 0.8 to 4.5 g / l nickel ions.
  • the method according to the invention is also applicable to such baths applicable.
  • the phosphating solutions contain Alkali metal and / or ammonium cations to determine the value of the free acid on the set the desired range.
  • Phosphating baths usually also contain so-called accelerators. These are substances associated with the pickling reaction on the metal surface resulting hydrogen react. This will prevent a so-called Polarization of the metal surface by covering with hydrogen.
  • the Accelerators thereby improve the even occupancy of the Metal surface with finely divided phosphate crystals, which are usually one size have between about 1 and about 10 microns.
  • the method according to the invention sets assuming that accelerators are not used which oxidize iron (II) to iron (III).
  • Hydroxylamine can be used as a free base, as a hydroxylamine-releasing compound for example hydroxylamine complexes and ketoximes or aldoximes or in Form of hydroxylammonium salts can be used.
  • a hydroxylamine-releasing compound for example hydroxylamine complexes and ketoximes or aldoximes or in Form of hydroxylammonium salts can be used.
  • One adds free Hydroxylamine is added to the phosphating bath or a phosphating bath concentrate it largely due to the acidic nature of these solutions Hydroxylammonium cation are present.
  • Hydroxylammonium salt the sulfates and the phosphates are particularly suitable. In the case of phosphates, the acid salts are due to the better solubility prefers.
  • the phosphating baths with not too much sulfate ions can advantageously a combination of free hydroxylamine and Hydroxylammonium sulfate can be used.
  • Hydroxylamine or its Compounds are added to the phosphating solution in such amounts that the calculated concentration of free hydroxylamine between about 0.1 to about 3 g / l, preferably between about 0.15 and about 1 g / l.
  • the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3- . Accordingly, the known fact that the pH values of the phosphating baths in the range from about 2.0 to about 3.6, which are in the acidic region, only a very small part of the phosphate is actually in the form is ignored when calculating or determining the concentration the triple negatively charged anions are present. At these pH values it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogen phosphate anion, together with undisociated phosphoric acid and with smaller amounts of double negatively charged hydrogen phosphate anions.
  • the phosphating of hot-dip galvanized steel strips is caused by fluoride ions relieved and also for the phosphating of electrolytically galvanized steel strip can the presence of fluoride ions for an even layer formation be beneficial. Accordingly, there is a further preferred embodiment of the Invention to use phosphating solutions that up to about 0.8 g / l fluoride in contain free or complex bound form. For example, for the Phosphating of electrolytically galvanized steel strip the preferred Fluoride levels in the range of 0.0 to about 0.5 g / l, especially in the range of about 0.1 to about 0.2 g / l.
  • phosphating solutions are generally prepared in the Known to those skilled in the art.
  • phosphate is in the form of Phosphoric acid introduced into the phosphating solutions.
  • the cations are in the form of acid-soluble compounds such as the carbonates, the oxides or the hydroxides of phosphoric acid are added so that they are partially neutralized becomes. Further neutralization to the desired pH range takes place preferably by adding sodium hydroxide or sodium carbonate.
  • Sources of free fluoride anions are, for example, sodium or Potassium fluoride.
  • tetrafluoroborate or Hexafluorosilicate can be used.
  • phosphating solutions that one Free acid content in the range of 0.4 to 4 points and a content of total acid in the range of 15 to 45 points.
  • the Terms "free acid” and “total acid” as well as their method of determination were used already explained above.
  • the values of the free acid are preferably between about 1.5 and about 3.5 and especially between about 2.0 and about 3.0 Points.
  • the total acid content is preferably in the range of about 25 up to about 35 points.
  • the temperature of the phosphating solution is in the process according to the invention preferably in the range from 50 to 70 ° C. and in particular between 53 and 65 ° C.
  • the one or both sides is galvanized Steel strip with the phosphating solution for a period in the range from 2 to 30 seconds in contact by placing the phosphating solution on the sprayed galvanized steel strip or by inserting the galvanized steel strip into the Dipping phosphating solution.
  • the spray treatment is technically simpler feasible and therefore preferred. Are particularly preferred Treatment times between 3 and 15 seconds.
  • the phosphating solution is treated with the galvanized steel strip Rinsed off water.
  • the process according to the invention assumes that iron (II) ions are not uncontrolled be entered into the phosphating solution. As already mentioned are therefore Prefer supplemental solutions that do not contain iron (II). Furthermore, at the phosphating of steel strip galvanized only on one side can be prevented that the non-galvanized steel side comes into contact with the phosphating solution and this get iron (II) ions into the phosphating solution by a pickling reaction. Accordingly, the process according to the invention is carried out in the case of Phosphating of one-sided galvanized steel strip in such a way that only the galvanized strip side in contact with the phosphating solution. You avoid through suitable technical measures such as a cover the non-galvanized side of the strip so that it comes into contact with the phosphating solution.
  • the process according to the invention is preferably used to produce phosphate layers with layer weights in the range from 1 to 2 g / m 2 .
  • the iron (II) ion content in the phosphating bath is adjusted so that layer weights of 1.5 ⁇ 0.3 g / m 2 are obtained.
  • the iron (II) ion content can be checked using known analytical techniques and particularly simply by immersing corresponding commercially available measuring strips in the treatment solution.
  • the metal surface Before applying the phosphating solution, the metal surface be completely water wettable. This is in continuous working Belt systems are usually given. If the belt surface is oiled this oil should be cleaned with a suitable cleaner before phosphating remove. The procedures for this are well known in the art.
  • activating agents Usually solutions or Suspensions used that contain titanium phosphates and sodium phosphates.
  • Phosphating process which is advantageously a passivating rinse follows. This takes place between phosphating and passivating Rinsing is usually an intermediate rinse with water. For one passivating rinsing are far from chromic acid treatment baths common.
  • chrome Replace passivation baths with chrome-free treatment baths.
  • pure inorganic bath solutions in particular based on hexafluorozirconates, or also organic reactive bath solutions, for example based on substituted ones Poly (vinylphenols) known.
  • Rinse solutions can also be used containing 0.001 to 10 g / l of one or more of the following cations: Lithium ions, copper ions, silver ions and / or bismuth ions.
  • the metal tapes phosphated according to the invention can be used directly with a organic coating. However, you can also start with unpainted condition after cutting, shaping and joining to components like Automobile bodies or household appliances are put together. The hereby associated forming processes are facilitated by the phosphate layer. Is the Corrosive stress on the finished components is low, such as at Household appliances can be made from the pre-phosphated metal assembled devices can be painted directly. For higher ones Corrosion protection requirements, such as those made in automotive engineering it is advantageous to do another one after assembling the bodies To follow phosphating treatment.
  • the values correspond to the commercially used phosphating process GRANODINE R 5854 (Henkel KGaA). Influence of the iron (II) content on the layer weight tape speed m / min Treatment time seconds Free acid points Total acidity points temperature ° C Fe (II) content mg / l layer weight g / m 2 Vergl.1 45 12 2.5 30 58 ⁇ 0 2.0 Beisp.1 45 12 2.5 30 58 20 1.7 Beisp.2 45 12 2.5 30 58 35 1.4 COMP.2 90 6 2.5 30 58 ⁇ 0 1.7 Beisp.3 90 6 2.5 30 58 20 1.5 Vergl.3 180 3 2.5 30 58 ⁇ 0 1.2 Beisp.4 180 3 2.5 30 58 20 1.1

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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Claims (8)

  1. Procédé de commande de poids de couche dans la phosphatation de rubans d'acier galvanisé sur une face ou sur les deux faces, avec une solution de phosphatation qui contient de 1 à 6 g/l d'ions zinc et de 10 à 30 g/l d'ions phosphate et qui possède une concentration en ions Fe(II) dans la zone de 3 à 100 mg/l,
    caractérisé en ce qu'
    en vue de réduire le poids de couche de 0,1 g/m2, on ajoute à la solution de phosphatation entre 3 et 20 mg/l d'ions Fe(II), et en vue d'augmenter le poids de couche de 0,1 g/m2 on retire de la solution de phosphatation entre 3 et 20 mg/l d'ions Fe(II) par oxydation en Fe(III).
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    la solution de phosphatation contient en supplément un ou plusieurs des cations suivants :
    1 à 5 g/l d'ions manganèse
    1 à 4 g/l d'ions magnésium
    o,8 à 4,5 g/l d'ions nickel.
  3. Procédé selon l'une quelconque des revendications 1 et 2,
    caractérisé en ce que
    la solution de phosphatation contient comme accélérateur, en supplément de 0,1 à 3 g d'hydroxylamine sous forme libre, ionisée ou liée.
  4. Procédé selon l'une quelconque des revendications 1 à 3,
    caractérisé en ce que
    la solution de phosphatation possède une concentration en acide libre dans la zone de 0,4 à 4 points et une concentration en acide total dans la zone de 15 à 45 points.
  5. Procédé selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce que
    la solution de phosphatation possède une température dans la zone de 50 à 70°C.
  6. Procédé selon l'une quelconque des revendications 1 à 5,
    caractérisé en ce qu'
    on met en contact la solution de phosphatation pendant un laps de temps dans la zone de 2 à 30 secondes par traitement par pulvérisation ou immersion avec le ruban d'acier galvanisé sur une face ou sur les deux faces.
  7. Procédé selon l'une quelconque des revendications 1 à 6,
    caractérisé en ce qu'
    on met en contact dans le cas de la phosphatation d'un ruban d'acier galvanisé d'un seul côté, seulement la face de la bande galvanisée avec la solution de phosphatation.
  8. Procédé selon l'une quelconque des revendications 1 à 7,
    caractérisé en ce qu'
    on produit des couches de phosphate ayant des poids de couche dans la zone de 1 à 2 g/m2.
EP99937820A 1998-03-02 1999-02-20 Commande de poids de couche lors de la phosphatation d'une bande Expired - Lifetime EP1090160B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19808755 1998-03-02
DE19808755A DE19808755A1 (de) 1998-03-02 1998-03-02 Schichtgewichtsteuerung bei Bandphosphatierung
PCT/EP1999/001108 WO1999045171A1 (fr) 1998-03-02 1999-02-20 Commande de poids de couche lors de la phosphatation d'une bande

Publications (2)

Publication Number Publication Date
EP1090160A1 EP1090160A1 (fr) 2001-04-11
EP1090160B1 true EP1090160B1 (fr) 2003-05-07

Family

ID=7859391

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99937820A Expired - Lifetime EP1090160B1 (fr) 1998-03-02 1999-02-20 Commande de poids de couche lors de la phosphatation d'une bande

Country Status (8)

Country Link
US (1) US6461450B1 (fr)
EP (1) EP1090160B1 (fr)
JP (1) JP2002505383A (fr)
KR (1) KR20010074665A (fr)
AT (1) ATE239807T1 (fr)
AU (1) AU3253499A (fr)
DE (2) DE19808755A1 (fr)
WO (1) WO1999045171A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3872621B2 (ja) * 1999-11-05 2007-01-24 新日本製鐵株式会社 自動車車体用亜鉛系メッキ鋼板
JP2001295063A (ja) * 2000-04-10 2001-10-26 Nippon Parkerizing Co Ltd 非鉄金属材料およびめっき鋼板へのりん酸塩被膜の形成方法
BR0207618B1 (pt) * 2001-02-26 2011-09-06 tubo de aço sem costura com superfìcie tratada, método de fabricação do tubo de aço e lìquido para tratamento por conversão quìmica para um tubo de aço.
US8062435B2 (en) * 2001-06-18 2011-11-22 Henkel Kommanditgesellschaft Auf Aktien Phosphating operation
AU2002361680A1 (en) * 2001-12-13 2003-07-09 Henkel Kommanditgesellschaft Auf Aktien Use of substituted hydroxylamines in metal phosphating processes
JP5119864B2 (ja) * 2006-10-31 2013-01-16 Ｊｆｅスチール株式会社 リン酸塩処理亜鉛系めっき鋼板及びその製造方法
DE102018202867A1 (de) * 2018-02-26 2019-08-29 Thyssenkrupp Ag Verfahren zur Anpassung, Homogenisierung und Aktivierung von Oberflächen mit dem Ziel verbesserter Oberflächeneigenschaften

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Publication number Priority date Publication date Assignee Title
DE3245411A1 (de) * 1982-12-08 1984-07-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
FR2569203B1 (fr) 1984-08-16 1989-12-22 Produits Ind Cie Fse Procede de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentre et bain utilises pour la mise en oeuvre de ce procede
JPS6220879A (ja) * 1985-07-18 1987-01-29 Nippon Kokan Kk <Nkk> 亜鉛メツキ装置による鋼板の片面化成処理方法
DE3537108A1 (de) 1985-10-18 1987-04-23 Collardin Gmbh Gerhard Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
JPH0660418B2 (ja) * 1987-03-26 1994-08-10 日本電装株式会社 リン酸塩化成処理液の酸化還元電位制御方法
DE3712339A1 (de) * 1987-04-11 1988-10-20 Metallgesellschaft Ag Verfahren zur phosphatierung vor der elektrotauchlackierung
US5236565A (en) 1987-04-11 1993-08-17 Metallgesellschaft Aktiengesellschaft Process of phosphating before electroimmersion painting
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
DE3927131A1 (de) 1989-08-17 1991-02-21 Henkel Kgaa Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
DE3927614A1 (de) 1989-08-22 1991-02-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metallen
DE4013483A1 (de) * 1990-04-27 1991-10-31 Metallgesellschaft Ag Verfahren zur phosphatierung von metalloberflaechen
US5268041A (en) 1990-04-27 1993-12-07 Metallgesellschaft Ag Process for phosphating metal surfaces
US5604040A (en) 1991-08-09 1997-02-18 Associated Universities, Inc. Zinc phosphate conversion coatings
DE4228470A1 (de) * 1992-08-27 1994-03-03 Henkel Kgaa Verfahren zur Phospatierung von einseitig verzinktem Stahlband
DE4241134A1 (de) * 1992-12-07 1994-06-09 Henkel Kgaa Verfahren zur Phosphatierung von Metalloberflächen
EP0717787B1 (fr) * 1993-09-06 1998-01-14 Henkel Kommanditgesellschaft auf Aktien Procede de phosphatage sans nickel
EP0653502A3 (fr) * 1993-11-11 1995-08-09 Nihon Parkerizing Article composite d'acier plaqué d'un métal contenant du zinc et procédé de production.
JPH08158061A (ja) * 1994-12-06 1996-06-18 Nippon Parkerizing Co Ltd 金属材料用りん酸亜鉛系化成処理液
FR2752851B1 (fr) * 1996-09-02 1998-11-13 Cfpi Ind Bain et procede de phosphatation de substrats metalliques, concentre pour la preparation de ce bain et substrats metalliques traites a l'aide de ces bain et procede
DE19639596A1 (de) 1996-09-26 1998-04-02 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
DE19740953A1 (de) 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband

Also Published As

Publication number Publication date
DE19808755A1 (de) 1999-09-09
AU3253499A (en) 1999-09-20
US6461450B1 (en) 2002-10-08
ATE239807T1 (de) 2003-05-15
EP1090160A1 (fr) 2001-04-11
WO1999045171A1 (fr) 1999-09-10
KR20010074665A (ko) 2001-08-08
DE59905477D1 (de) 2003-06-12
JP2002505383A (ja) 2002-02-19

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