EP0866888A1 - Method of phosphating metal surfaces - Google Patents

Method of phosphating metal surfaces

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Publication number
EP0866888A1
EP0866888A1 EP96938047A EP96938047A EP0866888A1 EP 0866888 A1 EP0866888 A1 EP 0866888A1 EP 96938047 A EP96938047 A EP 96938047A EP 96938047 A EP96938047 A EP 96938047A EP 0866888 A1 EP0866888 A1 EP 0866888A1
Authority
EP
European Patent Office
Prior art keywords
metal surfaces
phosphating
phosphating solutions
contact
brought
Prior art date
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Granted
Application number
EP96938047A
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German (de)
French (fr)
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EP0866888B1 (en
Inventor
Horst Gehmecker
Thomas Kolberg
Rüdiger Rein
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Chemetall GmbH
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Metallgesellschaft AG
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Publication of EP0866888A1 publication Critical patent/EP0866888A1/en
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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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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

Definitions

  • the invention relates to a method for phosphating at least partially iron or steel metal surfaces according to the low zinc technology and its use for preparing the metal surfaces for electrocoating, in particular for cathodic electrocoating.
  • the zinc phosphating process is widely used in the metalworking industry. As a pretreatment for painting, phosphating processes that use low-zinc technology bring special advantages.
  • the phosphating solutions used here contain zinc in concentrations of only about 0.4 to 2 g / 1 and produce phosphate layers on steel which offer very good paint adhesion and high resistance to paint infiltration when exposed to corrosion.
  • REPLACEMENT BLA ⁇ (RULE 26) Proven nitro compounds. These baths deliver high-quality, uniformly covering phosphate layers in a short time. It is also known to use peroxides as accelerators in low-zinc phosphating baths. Although these would be preferable to the use of the aforementioned accelerators for reasons of workplace hygiene and environmental protection, they are
  • EP-A-414296 proposes a method for phosphating iron and steel surfaces according to the low zinc technology with nitrite-free, zinc, phosphate and nitrate-containing phosphating solutions, in which the weight ratio of free P 2 O s increases Total P 2 0 5 is set to a value in the range from 0.04 to 0.2.
  • H 2 0 2 or alkali perborate should be added to the phosphating solution in such an amount that - in the incorporated state - the maximum peroxide concentration 17 mg / l (calculated as H 2 0 2 ) or the maximum Fe (II) concentration 60 mg / l (calculated as Fe).
  • REPLACEMENT BLA ⁇ (RULE 26) given up. Phosphate layers with a relatively low layer weight and a coarse crystalline structure are also obtained. In addition, if zinc is present at the same time, specks are formed on zinc surfaces, in particular because of the nitrate content. In the presence of aluminum, no crystalline phosphate layers can be created on the aluminum surfaces.
  • the object of the invention is to provide a method for the phosphating of at least partially iron or steel metal surfaces, which leads to sufficiently thick and fine crystalline phosphate layers, with possible simultaneous presence of zinc and / or aluminum surfaces, also leads to perfect phosphate layers thereon and the has no disadvantage associated with the addition of chlorate.
  • the object is achieved in that, according to the invention, a method of the type mentioned at the outset is used, in which the metal surfaces are kept at from 30 to 65 ° C. for from 1 to 8 minutes. in contact with aqueous acid phosphating solutions, the
  • Contain that are free of chlorate and added nitrite in which the weight ratio of free P 2 0 5 to total P 2 0 5 to a value in the range of 0.03 to 0.20 and the content of Free acid is set to a value in the range of 0.5 to 2.5.
  • Free of added nitrite means that no nitrite should be added to the phosphating solutions, but - if the process is designed with the addition of nitrate - low levels may be present due to formation from nitrate.
  • the method according to the invention is intended in particular for the surface treatment of iron and steel.
  • galvanized steel e.g. steel coated with ZnAl, ZnFe and ZnNi, aluminized steel, aluminum, zinc and their alloys.
  • alloy galvanized steel i.e. e.g. steel coated with ZnAl, ZnFe and ZnNi, aluminized steel, aluminum, zinc and their alloys.
  • Oxidizing agents are called hydrogen peroxide or peroxide compounds. Apart from the fact that in addition to H 2 0 2 or peroxide compounds, various other oxidizing agents are designated as suitable, it is emphasized as a particular advantage of the process that it leaves steel sides shiny metallic on substrates galvanized on one side. Because of this, it was to be expected that phosphating solutions which contain peroxide and formic acid and which work according to the low-zinc technology would not be able to produce flawless, high-quality phosphate layers on surfaces of iron and steel. In particular, it was not to be assumed that the use of formic acid would significantly increase the rate of phosphating.
  • the phosphating process according to EP-A-361375 also provides for adding phosphating solutions, which preferably work in accordance with the low-zinc technology, to formic acid, optionally in combination with nitrate, chlorate, nitrite and nitrobenzenesulfonate.
  • phosphating solutions which preferably work in accordance with the low-zinc technology
  • formic acid optionally in combination with nitrate, chlorate, nitrite and nitrobenzenesulfonate.
  • the purpose of the addition of formic acid is to produce phosphate coatings with relatively high nickel contents when using nickel-containing phosphating solutions, even if the nickel concentration in the phosphating solution is comparatively low. Also from this prior art it could not be deduced that the advantages obtained with the method according to the invention can be achieved.
  • Phosphating solutions contain nitrate up to a concentration of 30 g / 1.
  • the weight ratio of Zn to P 2 0 5 in the phosphating solution is preferably (0.023 to 0.14): 1.
  • the rule applies that ratios in the above range for higher bath temperatures and / or zinc concentrations and ratios in the lower range for lower bath temperatures and / or zinc concentrations are.
  • a preferred embodiment of the method according to the invention provides for the metal surfaces to be brought into contact with phosphating solutions which contain 0.01 to 0.1 g / 1 peroxide (calculated as H 2 O 2 ) and 0.3 to 2.5 g / 1 Formate (calc. As formation) included.
  • the surfaces are brought into contact with phosphating solutions which additionally contain up to 3 g / 1 manganese, magnesium, calcium, lithium, tungstate, vanadate, molybdate, optionally also nickel and / or cobalt or combinations thereof . From the point of view of workplace hygiene and environmental protection, however, addition of nickel and / or cobalt should be avoided. It is also expedient to add up to 0.030 g / 1 copper to the phosphating solutions
  • REPLACEMENT BLA ⁇ (RULE 26) the addition can be carried out alone or in combination with the aforementioned cations.
  • the phosphating solutions additionally contain manganese and / or magnesium and / or calcium and also nickel and / or cobalt, the weight ratio of Mn: Zn, of Mg: Zn and Ca: Zn, possibly of (Ni + Co) should be a maximum of 2: 1.
  • the fluoborate in quantities up to 3 g / 1 (calc. As BF 4 ) and / or fluosilicate in quantities up to 3 g / 1 (calc. As SiFj and / or simple fluoride in quantities up to 1 , 5 g / 1 (calc. As F)
  • the anions fluoborate, fluosilicate and / or fluoride generally increase the rate of phosphating and are also particularly advantageous when the treatment of aluminum-containing zinc surfaces is intended. For the crystalline phosphating of aluminum and the presence of free fluoride is essential for these alloys.
  • the process according to the invention is carried out in the temperature range from 30 to 65 ° C. Below 30 ° C the phosphating speed is generally no longer sufficient for modern series production, while at higher temperatures disadvantages, e.g. can occur due to increased system incrustation.
  • the process according to the invention can be carried out in spraying, dipping, spray-dipping or flooding. If that
  • the zinc concentration should be 0.4 to 1.2 g / 1.
  • a concentration of zinc in the range from 1.0 to 2.0 g / 1 is advantageous.
  • Zinc carbonate, zinc oxide and / or carbonates of the other optionally added cations are expediently used to adjust the content of the phosphating solution, which is essential to the invention, with regard to the free acid and the ratio of free P 2 O s to total P 2 0 5 .
  • the rinsing stages which are expediently designed as a rinsing bath cascade, work in the last rinsing bath with salt-free or low-salt water, which is supplied to the phosphating bath in the opposite direction from the rinsing stage to rinsing stage.
  • the phosphating bath it complements the above-mentioned dehydration of the phosphating solution.
  • the water extracted from the phosphating bath for example by reverse osmosis and electrodialysis, can be returned to the rinsing stages.
  • the pretreatment of the metals before the actual phosphating is done in a conventional manner.
  • degreasing can be carried out using aqueous, alkaline cleaners which expediently contain surfactant.
  • a pickling treatment e.g. with sulfuric acid, phosphoric acid or hydrochloric acid.
  • the workpieces can be known to form fine crystalline phosphate coatings prior to phosphating, e.g. with an activation bath containing titanium phosphate.
  • the phosphating treatment After the phosphating treatment, it is usually rinsed with water.
  • water For the purpose of improving corrosion protection, e.g. be treated with rinse solutions containing or containing chromic acid.
  • demineralized water instead of the aforementioned rinsing, one is carried out with demineralized water which has been adjusted to a pH in the range from 3.6 to 5.0 with mineral acid.
  • the phosphate coatings produced by the process according to the invention can be used in all fields in which phosphate coatings are used. However, it is of particular advantage in the phosphating of metal surfaces for the subsequent painting, in particular the subsequent electrocoating. The preparation process for cathodic electrocoating is particularly important.
  • Solution A 1.0 g / 1 Zn 0.7 points free acid
  • Solution B Solution A, but without formate
  • compositions were selected for the phosphating solutions for use in the dipping process
  • Solution C 1.8 g / 1 Zn 1.6 points free acid 1.0 g / 1 Mn 25 points total acid 13.0 g / 1 P 2 0 5 0.05 g / 1 H 2 0 2 1.0 g / 1 formate 3.0 g / 1 N0 3 alkali to adjust the free acidity
  • Solution D as solution C, but with 2.5 g / 1 C10 3 instead of formate
  • Solution E as solution C, but without formate
  • REPLACEMENT BLA ⁇ (RULE 26) activated and phosphated at 55 ° C in solutions C to E for 3 min while diving.
  • the layer weight, the crystal size, the minimum phosphating time and, after coating with cathodic electrocoat, filler and topcoat, the adhesion and resistance to infiltration were measured. The following results were obtained.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention concerns a method of phosphating metal surfaces consisting at least partially of iron or steel using low-zinc technology, in which the metal surfaces are brought into contact with aqueous acidic phosphating solutions at between 30 and 65 °C for between 1 and 8 minutes. The phosphating solutions contain: between 0.4 and 2.0 g/l Zn; between 7 and 25 g/l P2O5; between 0.005 and 0.5 g/l peroxide (calculated as H2O2); and between 0.01 and 10 g/l formiate (calculated as formiate ion). The phosphating solutions are free from chlorate and added nitrite, the weight ratio of free P2O5 to total P2O5 therein is set at a value of between 0.03 and 0.20, and the amount of free acid is set at a value of between 0.5 and 2.5. Additionally, the phosphating solutions can contain up to 30 g/l nitrate and manganese, magnesium, calcium, lithium, tungstate, vanadate, molybdate or combinations thereof, optionally also nickel and/or cobalt each in amounts of up to 3 g/l, and optionally also up to 0.030 g/l copper. The weight ratios of Mn : Zn, Mg : Zn, Ca : Zn and optionally of Ni and/or Co : Zn should be at most 2 : 1 in each case. The method is suitable in particular for preparing metal surfaces for subsequent electrophoretic enamelling, in particular cathodic electrophoretic enamelling.

Description

Verfahren zur Phosphatierunα von Metalloberflächen Process for phosphating metal surfaces
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Phosphatierung von mindestens teilweise aus Eisen oder Stahl bestehenden Metalloberflächen gemäß der Niedrigzink-Technologie sowie dessen Anwendung zur Vorbereitung der Metalloberflachen für die Elektrotauchlackierung, insbesondere für die kathodische Elektrotauchlackierung.The invention relates to a method for phosphating at least partially iron or steel metal surfaces according to the low zinc technology and its use for preparing the metal surfaces for electrocoating, in particular for cathodic electrocoating.
In der metallverarbeitenden Industrie wird in großem Umfang das Verfahren der Zinkphosphatierung angewendet. Als Vorbehandlung für die Lackierung bringen Phosphatierverfahren, die von der Niedrigzink-Technologie Gebrauch machen, besondere Vorteile. Die hierbei verwendeten Phosphatierungslösungen enthalten Zink in Konzentrationen von nur etwa 0,4 bis 2 g/1 und erzeugen auf Stahl Phosphatschichten, die eine sehr gute Lackhaftung und hohe Beständigkeit gegen Lackunterwanderung bei Korrosionsbeanspruchung bieten.The zinc phosphating process is widely used in the metalworking industry. As a pretreatment for painting, phosphating processes that use low-zinc technology bring special advantages. The phosphating solutions used here contain zinc in concentrations of only about 0.4 to 2 g / 1 and produce phosphate layers on steel which offer very good paint adhesion and high resistance to paint infiltration when exposed to corrosion.
Als Beschleuniger in Niedrigzink-Phosphatierbadern haben sich insbesondere Nitrit und Chlorat sowie organischeNitrite and chlorate, as well as organic ones, have proven to be accelerators in low-zinc phosphating baths
ERSATZBLAπ(REGEL26) Nitroverbindungen bewährt. Diese Bäder liefern in kurzer Zeit qualitativ hochwertige, gleichmäßig deckende Phosphatschichten. Auch ist es bekannt, in Niedrigzink-Phosphatierbadern Peroxide als Beschleuniger einzusetzen. Diese wären aus Gründen der Arbeitsplatzhygiene und des Umweltschutzes dem Einsatz der vorgenannten Beschleuniger zwar vorzuziehen, doch ist ihreREPLACEMENT BLAπ (RULE 26) Proven nitro compounds. These baths deliver high-quality, uniformly covering phosphate layers in a short time. It is also known to use peroxides as accelerators in low-zinc phosphating baths. Although these would be preferable to the use of the aforementioned accelerators for reasons of workplace hygiene and environmental protection, they are
Oxydationswirkung hinsichtlich der Oxydation von Eisen(II) zu Eisen(III) sehr stark. Dies führt dazu, daß auch bei langer Behandlungszeit vergleichsweise dünne Phosphatschichten mit nur mäßigem Korrosionsschutz zu erzielen sind.Oxidation effect with regard to the oxidation of iron (II) to iron (III) very strong. This means that comparatively thin phosphate layers with only moderate corrosion protection can be achieved even with a long treatment time.
Um dieses Problem zu lösen, wird in EP-A-414296 ein Verfahren zur Phosphatierung von Eisen- und Stahloberflächen gemäß der Niedrigzink-Technologie mit nitritfreien, Zink, Phosphat und Nitrat enthaltenden Phosphatierungεlösungen vorgeschlagen, in denen das Gewichtsverhaltnis von Freiem P2Os zu Gesamt-P205 auf einen Wert im Bereich von 0,04 bis 0,2 eingestellt iεt. Der Phosphatierungslösung soll H202 oder Alkaliperborat in einer solchen Menge zugegeben werden, daß -in eingearbeitetem Zustand- die maximale Peroxidkonzentration 17 mg/l (ber. als H202) bzw. die maximale Fe (II) -Konzentration 60 mg/l (ber. als Fe) beträgt.To solve this problem, EP-A-414296 proposes a method for phosphating iron and steel surfaces according to the low zinc technology with nitrite-free, zinc, phosphate and nitrate-containing phosphating solutions, in which the weight ratio of free P 2 O s increases Total P 2 0 5 is set to a value in the range from 0.04 to 0.2. H 2 0 2 or alkali perborate should be added to the phosphating solution in such an amount that - in the incorporated state - the maximum peroxide concentration 17 mg / l (calculated as H 2 0 2 ) or the maximum Fe (II) concentration 60 mg / l (calculated as Fe).
Bei dem vorgenannten Verfahren kann jedoch der Nachteil auftreten, daß die Phosphatierungsgeschwindigkeit für manche technische Anwendungsfälle nicht ausreicht. In der Praxis iεt man deshalb dazu übergegangen, die Phosphatiergeschwindigkeit durch Zusatz von Chlorat zu erhöhen. Damit wird jedoch ein wesentlicher Vorteil des vorgenannten Verfahrens wiederHowever, the disadvantage of the aforementioned process is that the rate of phosphating is not sufficient for some technical applications. In practice, one has therefore started to increase the rate of phosphating by adding chlorate. However, this again represents a major advantage of the aforementioned method
ERSATZBLAπ(REGEL26) aufgegeben. Auch werden Phosphatschichten mit relativ niedrigem Schichtgewicht und grobkristalliner Struktur erhalten. Hinzu kommt, daß bei gleichzeitiger Anwesenheit von Zink insbesondere wegen des Gehaltes an Nitrat auf Zinkoberflächen Stippen gebildet werden. Bei Anwesenheit von Aluminium können zudem auf den Aluminiumoberflächen keine kristallinen Phosphatschichten erzeugt werden.REPLACEMENT BLAπ (RULE 26) given up. Phosphate layers with a relatively low layer weight and a coarse crystalline structure are also obtained. In addition, if zinc is present at the same time, specks are formed on zinc surfaces, in particular because of the nitrate content. In the presence of aluminum, no crystalline phosphate layers can be created on the aluminum surfaces.
Aufgabe der Erfindung ist eε, ein Verfahren für die Phosphatierung von mindestens teilweise aus Eisen oder Stahl bestehenden Metalloberflächen bereitzustellen, das zu ausreichend dicken und feinkristallinen Phosphatschichten führt, bei eventueller gleichzeitiger Anwesenheit von Zink- und/oder Aluminiumoberflächen auch hierauf zu einwandfreien Phosphatschichten führt und den mit dem Zusatz von Chlorat verbundenen Nachteil nicht aufweist.The object of the invention is to provide a method for the phosphating of at least partially iron or steel metal surfaces, which leads to sufficiently thick and fine crystalline phosphate layers, with possible simultaneous presence of zinc and / or aluminum surfaces, also leads to perfect phosphate layers thereon and the has no disadvantage associated with the addition of chlorate.
Die Aufgabe wird gelöst, indem entsprechend der Erfindung ein Verfahren der eingangs genannten Art zum Einsatz gelangt, bei dem man die Metalloberflächen bei 30 bis 65°C für die Dauer von 1 bis 8 min. mit wäßrigen sauren Phosphatierungslösungen in Berührung bringt, dieThe object is achieved in that, according to the invention, a method of the type mentioned at the outset is used, in which the metal surfaces are kept at from 30 to 65 ° C. for from 1 to 8 minutes. in contact with aqueous acid phosphating solutions, the
o, ,4 bis 2,0 g/1 Zno., 4 to 2.0 g / 1 Zn
7 bis 25 g/1 P205 7 to 25 g / 1 P 2 0 5
0, 005 bis 0,5 g/1 Peroxid (ber. als H202)0.005 to 0.5 g / 1 peroxide (calc. As H 2 0 2 )
0, 01 bis 10 g/1 Formiat (ber. alε Formiation)0.01 to 10 g / 1 formate (calculated as formation)
enthalten, die frei von Chlorat und zugesetztem Nitrit sind, in denen das Gewichtsverhältnis von Freiem P205 zu Gesamt-P205 auf einen Wert im Bereich von 0,03 bis 0,20 und der Gehalt an Freier Säure auf einen Wert im Bereich von 0,5 bis 2,5 eingestellt ist.Contain that are free of chlorate and added nitrite, in which the weight ratio of free P 2 0 5 to total P 2 0 5 to a value in the range of 0.03 to 0.20 and the content of Free acid is set to a value in the range of 0.5 to 2.5.
Frei von zugesetztem Nitrit bedeutet, daß den Phosphatierungslösungen kein Nitrit zugegeben werden soll, sondern -bei Ausgestaltung des Verfahrens mit Nitratzugabe¬ alienfalls geringe Gehalte durch Bildung aus Nitrat vorliegen können.Free of added nitrite means that no nitrite should be added to the phosphating solutions, but - if the process is designed with the addition of nitrate - low levels may be present due to formation from nitrate.
Zur Bestimmung der Freien Säure, des Freien P205 sowie des Gesamt-P205 wird auf Rausch, Die Phosphatierung von Metallen, Leuze-Verlag/Saalgau 1988, Seiten 300 bis 304 verwiesen.To determine the free acid, the free P 2 0 5 and the total P 2 0 5 , reference is made to Rausch, Die Phosphatierung von Metallen, Leuze-Verlag / Saalgau 1988, pages 300 to 304.
Das erfindungsgemäße Verfahren ist insbesondere für die Oberflächenbehandlung von Eisen und Stahl bestimmt. Gemeinsam mit Eisen und Stahl können jedoch auch verzinkter Stahl, legierungsverzinkter Stahl, d.h. z.B. mit ZnAl, ZnFe und ZnNi beschichteter Stahl, aluminierter Stahl, Aluminium, Zink und deren Legierungen behandelt werden.The method according to the invention is intended in particular for the surface treatment of iron and steel. However, together with iron and steel, galvanized steel, alloy galvanized steel, i.e. e.g. steel coated with ZnAl, ZnFe and ZnNi, aluminized steel, aluminum, zinc and their alloys.
Zwar ist es aus WO 94/13856 bekannt, zur Phosphatierung von Metalloberflächen, insbesondere von verzinkten oder legierungsverzinkten Stahlbändern, bei Behandlungszeiten von 2 bis 20 see. Phosphatierungsbäder einzusetzen, die neben Zink, Phosphat und bestimmten Gehalten an Freier Säure und Gesamt- Säure wasserlösliche, organische Säuren enthalten, die einen zwischen den Dissoziationskonstanten der ersten und der zweiten Stufe der im Phosphatierbad enthaltenen Phosphorsäure liegenden pK-Wert für die erste Dissoziationεkonstante aufweisen, wobei als ein Beispiel für geeignete organische Säuren Ameisensäure und als ein Beispiel ein zusätzlichesIt is known from WO 94/13856 for the phosphating of metal surfaces, in particular of galvanized or alloy-galvanized steel strips, with treatment times of 2 to 20 seconds. To use phosphating baths which, in addition to zinc, phosphate and certain free acid and total acid contents, contain water-soluble organic acids which have a pK value for the first dissociation constant between the dissociation constants of the first and second stages of the phosphoric acid contained in the phosphating bath, with formic acid as an example of suitable organic acids and an additional one as an example
ERSATZBLAπ(REGEL26) Oxidationsmittel Wasserstoffperoxid oder Peroxidverbindungen genannt sind. Abgesehen davon, daß neben H202 oder Peroxidverbindungen diverse andere Oxidationsmittel als geeignet bezeichnet sind, wird als besonderer Vorteil des Verfahrens herausgeεtellt, daß es bei einseitig verzinkten Substraten metallisch blanke Stahlseiten hinterläßt. Aufgrund dessen war zu erwarten, daß Phosphatierungslösungen, die Peroxid und Ameisensäure enthalten und gemäß der Niedrigzink-Technologie arbeiten, nicht in der Lage sein würden, auch auf Oberflächen von Eisen und Stahl einwandfreie, qualitativ hochwertige Phosphatschichten zu erzeugen. Insbesondere war nicht anzunehmen, daß durch die Mitverwendung von Ameisensäure die Phosphatiergeschwindigkeit beträchtlich erhöht wird.REPLACEMENT BLAπ (RULE 26) Oxidizing agents are called hydrogen peroxide or peroxide compounds. Apart from the fact that in addition to H 2 0 2 or peroxide compounds, various other oxidizing agents are designated as suitable, it is emphasized as a particular advantage of the process that it leaves steel sides shiny metallic on substrates galvanized on one side. Because of this, it was to be expected that phosphating solutions which contain peroxide and formic acid and which work according to the low-zinc technology would not be able to produce flawless, high-quality phosphate layers on surfaces of iron and steel. In particular, it was not to be assumed that the use of formic acid would significantly increase the rate of phosphating.
Auch das Phosphatierverfahren gemäß EP-A-361375 sieht vor, Phoεphatierungεlösungen, die vorzugsweise entsprechend der Niedrigzink-Technologie arbeiten, Ameisensäure, gegebenenfalls in Kombination mit Nitrat, Chlorat, Nitrit und Nitrobenzolsulfonat, zuzusetzen. Zweck deε Zusatzes an Ameisensäure ist, bei Einsatz von nickelhaltigen Phosphatierungslösungen Phosphatüberzüge mit relativ hohen Nickelanteilen zu erzeugen, selbst wenn die Nickelkonzentration in der Phosphatierungslöεung vergleichsweise niedrig ist. Auch aus diesem Stand der Technik war nicht herleitbar, daß die mit dem erfindungsgemäßen Verfahren erhaltenen Vorteile erzielbar sind.The phosphating process according to EP-A-361375 also provides for adding phosphating solutions, which preferably work in accordance with the low-zinc technology, to formic acid, optionally in combination with nitrate, chlorate, nitrite and nitrobenzenesulfonate. The purpose of the addition of formic acid is to produce phosphate coatings with relatively high nickel contents when using nickel-containing phosphating solutions, even if the nickel concentration in the phosphating solution is comparatively low. Also from this prior art it could not be deduced that the advantages obtained with the method according to the invention can be achieved.
Gemäß einer bevorzugten Ausgestaltung der Erfindung können die im erfindungsgemaßen Verfahren eingesetzten Phosphatierungεlösungen Nitrat bis zu einer Konzentration von 30 g/1 enthalten.According to a preferred embodiment of the invention, those used in the method according to the invention can be used Phosphating solutions contain nitrate up to a concentration of 30 g / 1.
Wie bei Verfahren der Niedrigzink-Technologie üblich, beträgt das Gewichtsverhältnis von Zn zu P205 in der Phosphatierungslösung vorzugsweise (0,023 bis 0,14) : 1.As is customary in methods of low zinc technology, the weight ratio of Zn to P 2 0 5 in the phosphating solution is preferably (0.023 to 0.14): 1.
Bei der Abstimmung der Art und Menge von Kationen und Anionen der im erfindungsgemäßen Verfahren zum Einsatz kommenden Phosphatierungεlösungen gilt als Regel, daß für höhere Badtemperaturen und/oder Zinkkonzentrationen Verhältniszahlen im oberen genannten Bereich und für niedrigere Badtemperaturen und/oder Zinkkonzentrationen Verhältniszahlen im unteren Bereich zu wählen sind.When coordinating the type and amount of cations and anions of the phosphating solutions used in the process according to the invention, the rule applies that ratios in the above range for higher bath temperatures and / or zinc concentrations and ratios in the lower range for lower bath temperatures and / or zinc concentrations are.
Eine bevorzugte Ausgestaltung des erfindungsgemäßen Verfahrens sieht vor, die Metalloberflächen mit Phosphatierungslösungen in Kontakt zu bringen, die 0,01 bis 0,1 g/1 Peroxid (ber. als H202) und 0,3 bis 2,5 g/1 Formiat (ber. als Formiation) enthalten.A preferred embodiment of the method according to the invention provides for the metal surfaces to be brought into contact with phosphating solutions which contain 0.01 to 0.1 g / 1 peroxide (calculated as H 2 O 2 ) and 0.3 to 2.5 g / 1 Formate (calc. As formation) included.
Gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung bringt man die Oberflächen mit Phosphatierungslösungen in Berührung, die zusätzlich bis zu je 3 g/1 Mangan, Magneεium, Calzium, Lithium, Wolframat, Vanadat, Molybdat, gegebenenfalls auch Nickel und/oder Cobalt oder Kombinationen hiervon enthalten. Auε Sicht der Arbeitsplatzhygiene und des Umweltschutzes sollte jedoch von einem Zusatz von Nickel und/oder Cobalt abgesehen werden. Auch ist es zweckmäßig, den Phosphatierungεlöεungen bis zu 0,030 g/1 Kupfer zuzusetzenAccording to a further advantageous embodiment of the invention, the surfaces are brought into contact with phosphating solutions which additionally contain up to 3 g / 1 manganese, magnesium, calcium, lithium, tungstate, vanadate, molybdate, optionally also nickel and / or cobalt or combinations thereof . From the point of view of workplace hygiene and environmental protection, however, addition of nickel and / or cobalt should be avoided. It is also expedient to add up to 0.030 g / 1 copper to the phosphating solutions
ERSATZBLAπ(REGEL26) wobei der Zusatz allein oder in Kombination mit den vorgenannten Kationen erfolgen kann.REPLACEMENT BLAπ (RULE 26) the addition can be carried out alone or in combination with the aforementioned cations.
Sofern die Phosphatierungεlöεungen zuεätzlich Mangan und/oder Magneεium und/oder Calzium gegebenenfallε auch Nickel und/oder Cobalt enthalten, sollte das Gewichtsverhältnis von Mn : Zn, von Mg : Zn und Ca : Zn, ggf. von (Ni + Co) maximal 2 : 1 sein.If the phosphating solutions additionally contain manganese and / or magnesium and / or calcium and also nickel and / or cobalt, the weight ratio of Mn: Zn, of Mg: Zn and Ca: Zn, possibly of (Ni + Co) should be a maximum of 2: 1.
Eine weitere vorteilhafte Auεführungεform der Erfindung besteht darin, die Metalloberflächen mitA further advantageous embodiment of the invention consists in the metal surfaces
Phosphatierungslösungen in Berührung zu bringen, die Fluoborat in Mengen bis zu 3 g/1 (ber. als BF4) und/oder Fluosilikat in Mengen bis zu 3 g/1 (ber. als SiFj und/oder einfaches Fluorid in Mengen bis zu 1,5 g/1 (ber. als F) enthalten. Die Anionen Fluoborat, Fluosilikat und/oder Fluorid erhöhen allgemein die Phosphatiergeschwindigkeit und sind außerdem insbesondere dann von Vorteil, wenn die Behandlung von aluminiumhaltigen Zinkoberflächen beabsichtigt ist. Für die kristalline Phosphatierung von Aluminium und desεen Legierungen ist die Anwesenheit von freiem Fluorid unerläßlich.Phosphating solutions in contact, the fluoborate in quantities up to 3 g / 1 (calc. As BF 4 ) and / or fluosilicate in quantities up to 3 g / 1 (calc. As SiFj and / or simple fluoride in quantities up to 1 , 5 g / 1 (calc. As F) The anions fluoborate, fluosilicate and / or fluoride generally increase the rate of phosphating and are also particularly advantageous when the treatment of aluminum-containing zinc surfaces is intended. For the crystalline phosphating of aluminum and the presence of free fluoride is essential for these alloys.
Das erfindungsgemäße Verfahren wird im Temperaturbereich von 30 bis 65°C durchgeführt. Unterhalb 30°C reicht die Phosphatiergeschwindigkeit für die moderne Serienfertigung im allgemeinen nicht mehr aus, während bei höheren Temperaturen Nachteile, z.B. durch verstärkte Anlagenverkrustung auftreten können.The process according to the invention is carried out in the temperature range from 30 to 65 ° C. Below 30 ° C the phosphating speed is generally no longer sufficient for modern series production, while at higher temperatures disadvantages, e.g. can occur due to increased system incrustation.
Das erfindungsgemäße Verfahren kann im Spritzen, Tauchen, Spritz-Tauchen oder Fluten durchgeführt werden. Sofern dasThe process according to the invention can be carried out in spraying, dipping, spray-dipping or flooding. If that
ERSATZBLAπ(REGEL26) Verfahren als Spritzverfahren eingesetzt wird, sollte die Zinkkonzentration 0,4 bis 1,2 g/1 betragen. Im Falle der Anwendung im Spritz-Tauch- oder Tauchverfahren ist eine Konzentration an Zink im Bereich von 1,0 bis 2,0 g/1 vorteilhaft .REPLACEMENT BLAπ (RULE 26) If the process is used as a spray process, the zinc concentration should be 0.4 to 1.2 g / 1. When used in the spray-immersion or immersion process, a concentration of zinc in the range from 1.0 to 2.0 g / 1 is advantageous.
Es iεt zweckmäßig, die Formiationen als Alkaliformiat, Ammoniumformiat oder freie Ameisensäure in die Phosphatierungslösung einzubringen. Zur Einstellung des erfindungswesentlichen Gehaltes der Phosphatierungslösung hinsichtlich der Freien Säure und hinsichtlich deε Verhältnisses von Freiem P2Os zu Gesamt P205 dienen zweckmäßigerweise Zinkcarbonat, Zinkoxid und/oder Carbonate der anderen gegebenenfalls zugesetzten Kationen.It is expedient to introduce the formations into the phosphating solution as alkali formate, ammonium formate or free formic acid. Zinc carbonate, zinc oxide and / or carbonates of the other optionally added cations are expediently used to adjust the content of the phosphating solution, which is essential to the invention, with regard to the free acid and the ratio of free P 2 O s to total P 2 0 5 .
Bei der Durchführung des erfindungsgemäßen Phosphatierverfahrens ist es zweckmäßig, denWhen carrying out the phosphating process according to the invention, it is advantageous to use the
Phosphatierungslösungen Wasser zu entziehen und durch Zugabe von Spülwasser der nachfolgenden Spülεtufe oder der nachfolgenden Spülstufen auszugleichen. Der Wasserentzug erfolgt beispielsweise durch Verdampfung, Umkehrosmose und/oder Elektrodialyse . Insbesondere bei der Verwendung von Wasserεtoffperoxid als Peroxid-Komponente gelingt es damit, das erfindungsgemäße Verfahren derart zu betreiben, daß keine mit Phosphat verunreinigten Abwässer aus dem Spülvorgang hinter der Phosphatierung anfallen. Die zweckmäßigerweise als Spülbadkaskade ausgebildeten Spülstufen arbeiten dabei im letzten Spülbad mit salzfreiem bzw. salzarmem Wasser, das dem Werkstückstrom entgegengerichtet von Spülstufe zu Spülstufe dem Phosphatierungsbad zugeführt wird. Im Phosphatierungsbad ergänzt es den oben erwähnten Wasserentzug der Phosphatierungslösung. Das z.B. durch Umkehrosmose und Elektrodialyse dem Phosphatierungsbad entzogene Wasser kann in die Spülstufen zurückgeführt werden.To remove phosphating solutions from water and to balance the subsequent rinsing stage or rinsing stages by adding rinsing water. The water is removed, for example, by evaporation, reverse osmosis and / or electrodialysis. In particular when using hydrogen peroxide as the peroxide component, it is possible to operate the method according to the invention in such a way that no waste water contaminated with phosphate from the rinsing process occurs after the phosphating. The rinsing stages, which are expediently designed as a rinsing bath cascade, work in the last rinsing bath with salt-free or low-salt water, which is supplied to the phosphating bath in the opposite direction from the rinsing stage to rinsing stage. In the phosphating bath it complements the above-mentioned dehydration of the phosphating solution. The water extracted from the phosphating bath, for example by reverse osmosis and electrodialysis, can be returned to the rinsing stages.
Die Vorbehandlung der Metalle vor der eigentlichen Phosphatierung geschieht in konventioneller Weise. Beispielsweise kann eine Entfettung mittels wässriger, alkalischer Reiniger, die zweckmäßigerweise Tensid enthalten, vorgenommen werden. Sofern vorhanden, εind Zunder oder Roεt durch eine Beizbehandlung, z.B. mit Schwefelsäure, Phosphorsäure oder Salzsäure, zu entfernen.The pretreatment of the metals before the actual phosphating is done in a conventional manner. For example, degreasing can be carried out using aqueous, alkaline cleaners which expediently contain surfactant. If present, tinder or roast are produced by a pickling treatment, e.g. with sulfuric acid, phosphoric acid or hydrochloric acid.
Obgleich nicht zwingend notwendig, können die Werkstücke vor der Phosphatierung zur Ausbildung feinkristalliner Phosphatüberzüge in an sich bekannterweise, z.B. mit einem Titanphosphat enthaltenden Aktivierungsbad, vorgespült werden.Although not absolutely necessary, the workpieces can be known to form fine crystalline phosphate coatings prior to phosphating, e.g. with an activation bath containing titanium phosphate.
Nach der Phosphatierbehandlung wird üblicherweise mit Wasser gespült. Zum Zweck der Verbesserung des Korrosionsschutzes kann z.B. mit Chromsäure enthaltenden oder chromsäurefreien Nachspüllösungen nachbehandelt werden. Besonders vorteilhaft ist es jedoch, wenn entsprechend einer weiteren vorteilhaften Ausgestaltung der Erfindung anstelle der vorgenannten Nachspülung eine solche mit vollentsalztem Wasser, das mit Mineralsäure auf einen pH-Wert im Bereich von 3,6 biε 5,0 eingestellt ist, vorgenommen wird.After the phosphating treatment, it is usually rinsed with water. For the purpose of improving corrosion protection, e.g. be treated with rinse solutions containing or containing chromic acid. However, it is particularly advantageous if, in accordance with a further advantageous embodiment of the invention, instead of the aforementioned rinsing, one is carried out with demineralized water which has been adjusted to a pH in the range from 3.6 to 5.0 with mineral acid.
Die nach dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge sind auf allen Gebieten, auf denen Phosphatüberzüge Verwendung finden, einsetzbar. Es ist jedoch von besonderem Vorteil bei der Phosphatierung von Metalloberflächen für die anschließende Lackierung, insbesondere die anschließende Elektrotauchlackierung. Dabei ist insbesondere das Verfahren zur Vorbereitung für die kathodische Elektrotauchlackierung von besonderer Bedeutung.The phosphate coatings produced by the process according to the invention can be used in all fields in which phosphate coatings are used. However, it is of particular advantage in the phosphating of metal surfaces for the subsequent painting, in particular the subsequent electrocoating. The preparation process for cathodic electrocoating is particularly important.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
Beispiel 1example 1
Für die Anwendung im Spritzverfahren wurden folgende Phosphatierungslösungen hergestellt:The following phosphating solutions were prepared for use in the spray process:
Lösung A: 1,0 g/1 Zn 0,7 Punkte Freie SäureSolution A: 1.0 g / 1 Zn 0.7 points free acid
1,0 g/1 Mn 23 Punkte Gesamtsäure 13, 0 g/1 P2051.0 g / 1 Mn 23 points total acid 13.0 g / 1 P205
0,05 g/1 H2020.05 g / 1 H202
1, 0 g/1 Formiat1.0 g / 1 formate
3,0 g/1 N03 Alkali zur Einstellung der Freien Säure3.0 g / 1 N0 3 alkali to adjust the free acid
Lösung B: Lösung A, jedoch ohne FormiatSolution B: Solution A, but without formate
In den Lösungen A und B wurden mit einem aktivierenden alkalischen Reiniger entfettete Stahlbleche im Spritzen 2 min bei 52°C behandelt. Gemessen wurde das Schichtgewicht, die Kristallgröße, die Mindestphosphatierzeit sowie -nach Lackierung mit einem kathodischen Elektrotauchlack, Füller und Decklack- die Haftung und Unterwanderungsbeständigkeit an einem anschließend angebrachten Ritz. Folgende Werte wurden gemesεen:In solutions A and B, degreased steel sheets were treated with an activating alkaline cleaner by spraying at 52 ° C. for 2 min. The layer weight, the crystal size, the minimum phosphating time and - after painting with a cathodic electrocoat, filler and topcoat - the adhesion and infiltration resistance were measured a subsequent Ritz. The following values were measured:
Beispiel 2Example 2
Für die Anwendung im Tauchverfahren wurden nachstehende Zusammensetzungen für die Phosphatierungslösungen gewähltThe following compositions were selected for the phosphating solutions for use in the dipping process
Lösung C: 1,8 g/1 Zn 1,6 Punkte Freie Säure 1,0 g/1 Mn 25 Punkte Gesamtsäure 13,0 g/1 P205 0,05 g/1 H202 1,0 g/1 Formiat 3,0 g/1 N03 Alkali zur Einstellung der Freien SäureSolution C: 1.8 g / 1 Zn 1.6 points free acid 1.0 g / 1 Mn 25 points total acid 13.0 g / 1 P 2 0 5 0.05 g / 1 H 2 0 2 1.0 g / 1 formate 3.0 g / 1 N0 3 alkali to adjust the free acidity
Lösung D: wie Lösung C, jedoch mit 2,5 g/1 C103 anεtelle von FormiatSolution D: as solution C, but with 2.5 g / 1 C10 3 instead of formate
Löεung E: wie Löεung C, jedoch ohne FormiatSolution E: as solution C, but without formate
Mit einem alkalischen Reiniger entfettete Stahlbleche wurden in einer kollodialeε Titanphoεphat enthaltenden LöεungSteel sheets degreased with an alkaline cleaner were placed in a solution containing colloidal titanium phosphate
ERSATZBLAπ(REGEL26) aktiviert und bei 55°C in den Lösungen C bis E 3 min im Tauchen phosphatiert. Gemessen wurden das Schichtgewicht, die Kriεtallgröße, die Mindestphosphatierzeit sowie -nach Beschichtung mit kathodischem Elektrotauchlack, Füller und Decklack- die Haftung und Unterwanderungsbeständigkeit. Folgende Resultate wurden erhalten.REPLACEMENT BLAπ (RULE 26) activated and phosphated at 55 ° C in solutions C to E for 3 min while diving. The layer weight, the crystal size, the minimum phosphating time and, after coating with cathodic electrocoat, filler and topcoat, the adhesion and resistance to infiltration were measured. The following results were obtained.

Claims

Patentansprüche claims
1. Verfahren zur Phoεphatierung von mindestens teilweise aus Eisen oder Stahl bestehenden Metalloberflächen gemäß der Niedrigzink-Technologie, bei dem man die Metalloberflächen bei 30 bis 65°C für die Dauer von 1 bis 8 min. mit wäßrigen sauren Phosphatierungslösungen in Berührung bringt, die1. A process for phosphating metal surfaces consisting at least partially of iron or steel according to the low-zinc technology, in which the metal surfaces are kept at 30 to 65 ° C. for a period of 1 to 8 minutes. in contact with aqueous acid phosphating solutions, the
0,4 biε 2, 0 g/1 Zn0.4 to 2.0 g / 1 Zn
7 bis 25 g/1 P205 7 to 25 g / 1 P 2 0 5
0,005 bis 0,5 g/1 Peroxid (ber. als H202)0.005 to 0.5 g / 1 peroxide (calculated as H 2 0 2 )
0,01 bis 10 g/1 Formiat (ber. als Formiation)0.01 to 10 g / 1 formate (calculated as formation)
enthalten, die frei von Chlorat und zugesetztem Nitrit sind, in denen das Gewichtsverhältnis von Freiem P205 zu Gesamt-P205 auf einen Wert im Bereich von 0,03 bis 0,20 und der Gehalt an Freier Säure auf einen Wert im Bereich von 0,5 biε 2,5 eingestellt iεt.Contain that are free of chlorate and added nitrite, in which the weight ratio of free P 2 0 5 to total P 2 0 5 to a value in the range of 0.03 to 0.20 and the content of free acid to a value is set in the range from 0.5 to 2.5.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberflächen mit Phosphatierungslösungen in Berührung bringt, die zusätzlich bis 30 g/1 Nitrat enthalten. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Metalloberflächen mit Phosphatierungslösungen in Berührung bringt, die2. The method according to claim 1, characterized in that the metal surfaces are brought into contact with phosphating solutions which additionally contain up to 30 g / 1 nitrate. 3. The method according to claim 1 or 2, characterized in that the metal surfaces are brought into contact with phosphating solutions which
0,010 bis 0,1 g/1 Peroxid (ber. als H202) und 0,0.010 to 0.1 g / 1 peroxide (calculated as H 2 0 2 ) and 0,
3 bis 2,5 g/1 Formiat (ber. als Formiation) enthalten.3 to 2.5 g / 1 formate (calc. As formation) included.
4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Metalloberflächen mit Phosphatierungslösungen in Berührung bringt, die zusätzlich Mangan, Magnesium, Calzium, Lithium, Wolframat, Vanadat, Molybdat oder Kombinationen hiervon, gegebenenfalls auch Nickel und/oder Cobalt in Mengen von jeweils bis zu 3 g/1 enthalten.4. The method according to claim 1, 2 or 3, characterized in that the metal surfaces are brought into contact with phosphating solutions which additionally contain manganese, magnesium, calcium, lithium, tungstate, vanadate, molybdate or combinations thereof, optionally also nickel and / or cobalt contained in amounts of up to 3 g / 1 each.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man die Metalloberflächen mit Phosphatierungslösungen in Kontakt bringt, in denen die Gewichtsverhältnisse Mn : Zn, Mg : Zn, Ca : Zn und gegebenenfalls von (Ni und/oder Co) : Zn jeweils maximal 2 : 1 betragen.5. The method according to claim 4, characterized in that the metal surfaces are brought into contact with phosphating solutions in which the weight ratios Mn: Zn, Mg: Zn, Ca: Zn and optionally of (Ni and / or Co): Zn in each case a maximum of 2 : 1 amount.
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Metalloberflächen mit Phosphatierungslösungen in Berührung bringt, die zusätzlich bis zu 0,030 g/1 Cu enthalten.6. The method according to one or more of claims 1 to 5, characterized in that the metal surfaces are brought into contact with phosphating solutions which additionally contain up to 0.030 g / 1 Cu.
ERSATZBLAπ(REGEL26) REPLACEMENT BLAπ (RULE 26)
7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Metalloberflächen mit Phosphatierungslösungen in Berührung bringt, die zusätzlich komplexe und/oder einfache Fluoride enthalten.7. The method according to one or more of claims 1 to 6, characterized in that the metal surfaces are brought into contact with phosphating solutions which additionally contain complex and / or simple fluorides.
8. Verfahren nach einem oder mehreren der Anεprüche 1 bis 7, dadurch gekennzeichnet, daß man die phosphatierten Metalloberflächen mit vollentsalztem Wasser, das mit Mineralsäure auf einen pH-Wert im Bereich von 3,6 biε 5,0 eingestellt ist, nachspült.8. The method according to one or more of claims 1 to 7, characterized in that the phosphated metal surfaces are rinsed with demineralized water which is adjusted to a pH in the range from 3.6 to 5.0 with mineral acid.
9. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 8 zur Vorbereitung von Metalloberflächen für die nachfolgende Elektrotauchlackierung, insbesondere die kathodische Elektrotauchlackierung.9. Application of the method according to one or more of claims 1 to 8 for the preparation of metal surfaces for the subsequent electrocoating, in particular the cathodic electrocoating.
ERSATZBLAπ(REGEL26) REPLACEMENT BLAπ (RULE 26)
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ZA969999B (en) 1998-05-28
AU702478B2 (en) 1999-02-25
MX9804278A (en) 1998-09-30
EP0866888B1 (en) 1999-06-16

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