EP0045110A1 - Method for the production of phosphate coatings on iron and steel surfaces, and its use - Google Patents

Method for the production of phosphate coatings on iron and steel surfaces, and its use Download PDF

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Publication number
EP0045110A1
EP0045110A1 EP81200830A EP81200830A EP0045110A1 EP 0045110 A1 EP0045110 A1 EP 0045110A1 EP 81200830 A EP81200830 A EP 81200830A EP 81200830 A EP81200830 A EP 81200830A EP 0045110 A1 EP0045110 A1 EP 0045110A1
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Prior art keywords
solution
weight
ratio
iron
contact
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EP81200830A
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German (de)
French (fr)
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EP0045110B1 (en
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Kevin Brown
Jon Darby
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Chemetall Ltd
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • 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
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate 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
    • C23C22/22—Orthophosphates containing alkaline earth metal cations

Definitions

  • the invention relates to a process for the production of phosphate coatings on iron or steel surfaces by immersion or flooding with an aqueous acidic zinc phosphate solution and its application to the preparation of metal surfaces for cold forming.
  • phosphate coatings on metal surfaces in particular from iron and steel, by treatment with a zinc phosphate solution is generally common.
  • one or more oxidizing agents are added to the phosphating solution.
  • phosphating processes uses phosphating solutions which contain oxidizing agents which convert iron (II) to iron (III), so that insoluble iron phosphate is formed. With increasing throughput on the surface, considerable amounts of sludge then arise, which are physically removed. In some processes, however, the physical removal of sludge is difficult or difficult to carry out, so that it is more advantageous to conduct the phosphating process in such a way that practically no or only a little sludge is formed.
  • the phosphating solution is formulated from chemicals that do not dilute the iron in solution to the trivalent state. This happens, for example, by using Naiofat or similarly weak oxidizing agents as accelerators.
  • urea is to be added to the phosphating bath, as a result of which the temperature during the phosphating can be increased without risking significantly increased sludge formation. This is also associated with an accelerated phosphate layer formation.
  • the other disadvantages mentioned above also remain here.
  • heating of the phosphating solution which is not per se energy-wasting, is required.
  • attempts have been made to solve the sludge problem by increasing its solids content and consequently reducing the amount of sludge (GB-PS 1 555 529).
  • the metal surfaces are treated with a solution which contains at least 6 g / 1 Zn, 5 g / 1 P 2 0 5 , 1 g / 1 C10 3 and 8 g / 1 N0 3 .
  • the ratio P 2 O 5 : Zn should be in the range of 1: (0.8 - 4).
  • the object of the invention is to provide a process for producing phosphate coatings on iron or steel surfaces which does not have the known, in particular the aforementioned disadvantages, and is simple to carry out without additional chemicals and without sacrificing layer quality.
  • the object is achieved by carrying out the method of the type mentioned at the outset in accordance with the invention in such a way that the surfaces are brought into contact with a solution which contains at least 0.3% by weight of Zn and at least 0.3% by weight of P0 4 and contains at least 0.75 wt .-% N0 3 or an equivalent iron (II) non-oxidizing accelerator ,. in which the weight ratio Zn: P0 4 is greater than 0.8, the ratio of total acid to free acid is at least 5 and in which an oxidizing accelerator is suitably dimensioned by C10 3 or an equivalent iron (II) to iron (III) Iron (II) content of 0.05 to 1 wt .-%.
  • An advantageous embodiment of the invention consists in bringing the surface into contact with a solution which contains a maximum of 2.2% by weight of Zn, max. 2.2% by weight of P0 4 and max. 5.5 wt .-% NO 3 or an equivalent accelerator, in which the weight ratio Zn: P0 4 is less than 4 and the ratio of total acid to free acid max. 30 is.
  • a treatment solution should preferably be used which contains 0.3 to 1% by weight of Zn, 0.3 to 1% by weight of P0 4 and 1 to 3% by weight of N0 3 or a co-accelerator in which the Weight ratio Zn: P0 4 in particular 0.8 to 1.4, and the ratio of total acid to free acid of max. 15, in particular. 12 has a suitable F (sem) content of 0.08 to 0.5, in particular up to 0.2,% by weight in the mar by suitable dimensioning of acceleration or an equivalent acceleration.
  • nitroguanidine is also suitable, for example.
  • the expenditure of chlorate or a similarly acting iron (II) to iron (III) oxidizing accelerator is such that its concentration in the treatment solution is generally less than 0.1% by weight (calc. than C10 3 ). Higher doses cause the iron (II) content to be too low and considerable sludge formation occurs.
  • a further development of the method provides for the surfaces to be brought into contact with a solution which additionally contains calcium in quantities of 0.01 to 0.88% by weight, preferably 0.15 to 0.5% by weight.
  • the weight ratio Zn: Ca 1.5bLs 4 should be. Best results are achieved with a ratio of 2.5.
  • the phosphating solution can also contain other additives which are customary for zinc phosphating solutions, such as copper, cobalt, nickel, simple or complex fluoride. When dosing with fluoride, make sure that no calcium fluoride fails. Magnesium can partially or completely replace calcium.
  • urea can be added to the phosphating solution.
  • the surfaces to be brought into contact with the method according to the invention must be free of rust and scale and should therefore first be pickled with mineral acid, such as hydrochloric or sulfuric acid, and then rinsed with water. Depending on the level of contamination, degreasing or other treatment can also be carried out to clean the surfaces, for example with an organic solvent or an alkaline cleaner, followed by a water rinse.
  • mineral acid such as hydrochloric or sulfuric acid
  • the cleaned surfaces can finally be subjected to an activation treatment, e.g. by hot water rinsing or with a titanium orthophosphate dispersion.
  • an activation treatment e.g. by hot water rinsing or with a titanium orthophosphate dispersion.
  • Dipping or flooding the surfaces which, unlike spraying, results in sludge formation due to oxidation Avoiding atmospheric oxygen to a large extent takes place according to a preferred embodiment of the method according to the invention at a temperature of 35 to 98 ° C, preferably 55 to 85 ° C.
  • the period of contact between the surface and the phosphating solution is preferably in the range from 5 to 15 minutes.
  • the phosphate coating After formation of the phosphate coating can be done with cold water and with a passivating rinse solution It can also have a lubricant coating on it Phosphatschicnt be applied.
  • the method according to the invention has in particular proven to be Proven for non-cutting cold forming. It is also with advantage in the other areas of application Use phosphating, e.g. for corrosion protection, to facilitate sliding friction and for electrical insulation.
  • a phosphating solution was prepared from a batch concentrate which contained and had a ratio of total acid to free acid of 7. The dilution was carried out in the ratio of one part of concentrate to 20 parts of water.
  • Wire was immersed in the phosphating bath kept at a temperature of 70 ° C. After a contact time of 10 minutes, the wire was removed, rinsed with water, provided with a lubricant coating and pulled in the usual way.
  • the phosphating bath could be kept practically constant at concentrations of Fur smaller than 0.2 wt .-% are kept.
  • the ratio of total acid to free acid was 8.7.
  • the process could be operated for a long time with only a small amount of sludge.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Materials For Medical Uses (AREA)
  • Glass Compositions (AREA)
  • Treatment Of Sludge (AREA)
  • Paints Or Removers (AREA)

Abstract

Phosphate coatings are formed on ferrous surfaces by dipping or flooding the surfaces with an acidic zinc phosphate solution containing a high zinc content, nitrate or other oxidising agent incapable of oxidising ferrous to ferric and a low controlled amount of chlorate or other oxidising agent capable of oxidising ferrous to ferric such that the solution contains 0.05 to 1% dissolved iron. This process can be achieved but using novel replenishment and make up solutions. The initial make up solution may be free of chlorate but the replenishment solution will contain a low amount of chlorate or other suitable oxidising agent. The phosphating solution preferably has a zinc/phosphate ratio in the range 0.8-4, a Zn/Ca ratio of 1-4 and a total acid/free acid ratio of 5-9. Use of the solution gives rise to reduced sludge production. The solution may contain conventional additives such as Cu, Co, Ni, fluorides, urea. The surfaces to be treated may first be pickled, degreased then preactivated with either hot water or a titanium ortho- phosphate dispersion.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Phosphatüberzügen auf Eisen- oder Stahloberflächen im Tauch- oder Flutverfahren mit einer wäßrigen sauren Zinkphosphatlösung sowie dessen Anwendung auf die Vorbereitung von Metalloberflächen für die Kaltverformung.The invention relates to a process for the production of phosphate coatings on iron or steel surfaces by immersion or flooding with an aqueous acidic zinc phosphate solution and its application to the preparation of metal surfaces for cold forming.

Die Herstellung von Phosphatüberzügen auf Metalloberflächen, insbesondere aus Eisen und Stahl, durch Behandlung mit einer Zinkphosphatlösung ist generell üblich. Zur Beschleunigung der Phosphatschichtausbildung werden dabei der Phosphatierungslösung ein oder mehrere Oxidationsmittel zugesetzt.The production of phosphate coatings on metal surfaces, in particular from iron and steel, by treatment with a zinc phosphate solution is generally common. To accelerate the formation of the phosphate layer, one or more oxidizing agents are added to the phosphating solution.

Ein besonderes Problem, das sich bei der Herstellung von Phosphatüberzügen auf Eisen- und Stahloberflächen stellt, ist die mit der Phosphatierung verbundene' Auflösung von Eisen, das in Form von Eisen(II)ionen in Lösung geht.A particular problem that arises in the production of phosphate coatings on iron and steel surfaces, is connected to the phosphating 'dissolution of iron, the ion in the form of iron (II) in solution.

Bei einer Kategorie von Phosphatierverfahren arbeitet man mit Phosphatierungslösungen, die Eisen(II) in Eisen(III) überführende Oxidationsmittel enthalten, so daß unlösliches Eisenphosphat gebildet wird. Mit zunehmendem Durchsatz an Oberfläche entstehen dann erhebliche Schlammengen, die physikalisch entfernt werden. Bei einigen Verfahren bereitet jedoch die physikalische Schlammentfernung Schwierigkeiten bzw. ist schwer durchführbar, so daß es vorteilhafter ist, das Phosphatierverfahren so zu leiten, daß praktisch kein oder nur wenig Schlamm gebildet wird.One category of phosphating processes uses phosphating solutions which contain oxidizing agents which convert iron (II) to iron (III), so that insoluble iron phosphate is formed. With increasing throughput on the surface, considerable amounts of sludge then arise, which are physically removed. In some processes, however, the physical removal of sludge is difficult or difficult to carry out, so that it is more advantageous to conduct the phosphating process in such a way that practically no or only a little sludge is formed.

Bei dieser Kategorie von Phosphatierverfahren, die "auf der Eisenseite" arboiten, wird die Phosphatierlösung aus Chemikalien formuliert, die das in Lösung gehende Eisen nicht in den dreiwertigen Eustand äbefünren. Dies galingt beispiels welse durch Verwendung von Naiofat oder ähnlich schwachen Oxidationsmitteln als Beschleuniger.In this category of phosphating processes, which work "on the iron side", the phosphating solution is formulated from chemicals that do not dilute the iron in solution to the trivalent state. This happens, for example, by using Naiofat or similarly weak oxidizing agents as accelerators.

Ghsleich bei den "auf der Eisonsoite" arbeitenden Finsplasti verfahren die Schlammbildung weitgehend unterdrückt ist, haiten ihnen andere Nachteile an. So ist infolge Abwesenheit suarker Oxidationsmittel die Phosphatschichtausbildung lang- sami. Durch die Anreicherung von Eisen(II)phosphat in der Lasung kann zudem der Anteil des Eisenphosphats in der gebildecen Phosphatschicht unerwünscht hoch werden. Auch neigen die gebildeten Phosphatschichten zur Grobkörnigkeit. Es hat nicht an Versuchen gefehlt, die verschiedenartigsten Probleme auszuräumen.At the same time that the sludge formation is largely suppressed in the Finsplasti working on the Eisonsoite, they have other disadvantages. Because of the absence of suaric oxidizing agents, the formation of phosphate layers is slow. Due to the accumulation of iron (II) phosphate in the solution, the proportion of iron phosphate in the formed phosphate layer can also become undesirably high. The phosphate layers formed also tend to be coarse. There has been no shortage of attempts to solve a wide variety of problems.

Aus der GB-PS 932 987 ist es bekannt, die Metalloberflächen vor der Phosphatierung durch Inkontaktbringen mit einer Titan enthaltenden Lösung zu aktivieren. Hierdurch wird die Phosphatschichtausbildung zwar beschleunigt, die anderen Nachteile bleiben jedoch bestehen. Insbesondere sind zusätzliche Behandlungsvorrichtungen nötig.From GB-PS 932 987 it is known to activate the metal surfaces prior to phosphating by contacting them with a solution containing titanium. This accelerates the formation of the phosphate layer, but the other disadvantages remain. In particular, additional treatment devices are necessary.

Bei dem Verfahren gemäß GB-PS 996 418 soll Harnstoff dem Phosphatierbad zugesetzt werden, wodurch die Temperatur bei der Phosphatierung erhöht werden kann, ohne eine wesentlich erhöhte Schlammbildung zu riskieren. Auch hiermit ist eine bescheunigte Phosphatschichtausbildung verbunden. Die anderen zuvorgenannten Nachteile bleiben jedoch auch hier bestehen. Darüber hinaus entsteht der zusätzliche Nachteil, daß eine an sich nicht erforderliche, energieverschwendende Aufheizung der Phosphatierungslösung erforderlich ist. Bei einem anderen, nicht "auf der Eisenseite" arbeitenden Bad hat man versucht, das Schlammproblem zu lösen, indem dessen Feststoffgehalt erhöht und infolgedessen die Schlammenge reduziert wird (GB-PS 1 555 529).In the process according to GB-PS 996 418, urea is to be added to the phosphating bath, as a result of which the temperature during the phosphating can be increased without risking significantly increased sludge formation. This is also associated with an accelerated phosphate layer formation. However, the other disadvantages mentioned above also remain here. In addition, there is the additional disadvantage that heating of the phosphating solution, which is not per se energy-wasting, is required. In another bath which does not work "on the iron side", attempts have been made to solve the sludge problem by increasing its solids content and consequently reducing the amount of sludge (GB-PS 1 555 529).

Hierzu werden die Metalloberflächen mit einer Lösung behandelt, die wenigstens 6 g/1 Zn, 5 g/1 P205, 1 g/1 C103 und 8 g/1 N03 enthalten. Das Verhältnis P2O5 : Zn soll dabei im Bereich von 1:(0,8 - 4) liegen. Obgleich bei diesem Verfahren ein kompakter Schlamm erhalten wird und demzufolge die Intervalle zwischen der erforderlichen Entschlammung der jeweiligen Behandlungsvorrichtung größer sind, hat sich gezeigt, daß es schwieriger sein kann, kompakten Schlamm anstelle von leichtem, voluminösem Schlamm zu entfernen.For this purpose, the metal surfaces are treated with a solution which contains at least 6 g / 1 Zn, 5 g / 1 P 2 0 5 , 1 g / 1 C10 3 and 8 g / 1 N0 3 . The ratio P 2 O 5 : Zn should be in the range of 1: (0.8 - 4). Although a compact sludge is obtained in this process and, consequently, the intervals between the required desludging of the respective treatment device are larger, it has been shown that it can be more difficult to remove compact sludge instead of light, voluminous sludge.

Aufgabe der Erfindung ist es, ein Verfahren zur Herstellung von Phosphatüberzügen auf Eisen- oder Stahloberflächen bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile nicht aufweist und ohne Mehraufwand an Chemikalien und ohne Einbuße in der Schichtqualität einfach in der Durchführung ist.The object of the invention is to provide a process for producing phosphate coatings on iron or steel surfaces which does not have the known, in particular the aforementioned disadvantages, and is simple to carry out without additional chemicals and without sacrificing layer quality.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart durchgeführt wird, daß man die Oberflächen mit einer Lösung in Berührung bringt, die mindestens 0,3 Gew.-% Zn, mindestens 0,3 Gew.-% P04 und mindestens 0,75 Gew.-% N03 oder eines gleichwirkenden Eisen(II) nicht oxidierenden Beschleunigers enthält,. in der das Gewichtsverhältnis Zn:P04 größer als 0,8 ist, das Verhältnis von Gesamtsäure zu Freier Säure mindestens 5 beträgt und in der man durch geeignete Bemessung von C103 oder einem gleichwirkenden Eisen(II) zu Eisen(III) oxidierenden Beschleuniger einen Eisen(II)-Gehalt von 0,05 bis 1 Gew.-% einstellt.The object is achieved by carrying out the method of the type mentioned at the outset in accordance with the invention in such a way that the surfaces are brought into contact with a solution which contains at least 0.3% by weight of Zn and at least 0.3% by weight of P0 4 and contains at least 0.75 wt .-% N0 3 or an equivalent iron (II) non-oxidizing accelerator ,. in which the weight ratio Zn: P0 4 is greater than 0.8, the ratio of total acid to free acid is at least 5 and in which an oxidizing accelerator is suitably dimensioned by C10 3 or an equivalent iron (II) to iron (III) Iron (II) content of 0.05 to 1 wt .-%.

Eine vorteilhafte'Ausgestaltung der Erfindung besteht darin, die Oberfläche mit einer Lösung in Berührung zu bringen, die maximal 2,2 Gew.-% Zn, max. 2,2 Gew.-% P04 und max. 5,5 Gew.-% NO3 oder eines gleichwirkenden Beschleunigers enthält, in der das Gewichtsverhältnis Zn:P04 kleiner als 4 ist und das Verhältnis von Gesamtsäure zu Freier Säure max. 30 beträgt.An advantageous embodiment of the invention consists in bringing the surface into contact with a solution which contains a maximum of 2.2% by weight of Zn, max. 2.2% by weight of P0 4 and max. 5.5 wt .-% NO 3 or an equivalent accelerator, in which the weight ratio Zn: P0 4 is less than 4 and the ratio of total acid to free acid max. 30 is.

Vorzugsweise sollte eine Behandlungslösung zum Einsatz kommen, die 0,3 bis 1 Gew.-% Zn, 0,3 bis 1 Gew.-% P04 und 1 bis 3 Gew.-% N03 oder eines gleichwickenden Beschleunigers enthält, in der das Gewichtsverhälthis Zn: P04

Figure imgb0001
inscesondere 0,8 bis 1,4, beträgt und die ein Verhälthis von Gesamtsäure zu Freier Säure von max. 15, insbesorders. 12 aufweist udn in der mar durch geeignete Bemassung von oder einem gleichwirkenden Beschleunigen eintn Fi- sem (II)-Gehalf von 0,08 bis 0,5, insbesondere bis 0,2, Gew.-% einstellt.A treatment solution should preferably be used which contains 0.3 to 1% by weight of Zn, 0.3 to 1% by weight of P0 4 and 1 to 3% by weight of N0 3 or a co-accelerator in which the Weight ratio Zn: P0 4
Figure imgb0001
in particular 0.8 to 1.4, and the ratio of total acid to free acid of max. 15, in particular. 12 has a suitable F (sem) content of 0.08 to 0.5, in particular up to 0.2,% by weight in the mar by suitable dimensioning of acceleration or an equivalent acceleration.

Auber Nitrat als Eisen(II) nicht oxidierender Beschleuniger ist beispielsweise auch Nitroguanidin geeignet.In addition to nitrate as an iron (II) non-oxidizing accelerator, nitroguanidine is also suitable, for example.

Zur Einstellung des Gehaltes an Eisen(II) ist der Aufwand an Chlorat oder einem gleichwirkenden Eisen(II) zu Eisen(III) oxidierenden Beschleuniger derart, daß dessen Konzentration in der Behandlungslösung im allgemeinen kleiner als 0,1 Gew.-% (ber. als C103) ist. Höhere Dosierungen bewirken, daß der Eisen(II)-Gehalt zu gering wird und eine erhebliche Schlammbildung auftritt.To adjust the iron (II) content, the expenditure of chlorate or a similarly acting iron (II) to iron (III) oxidizing accelerator is such that its concentration in the treatment solution is generally less than 0.1% by weight (calc. than C10 3 ). Higher doses cause the iron (II) content to be too low and considerable sludge formation occurs.

Die besten Ergebnisse werden erzielt, wenn der Gehalt an Chlorat oder einem gleichwirkenden Beschleuniger auf Konzentrationen unter 0,05 Gew.-%, vorzugsweise unter 0,035 Gew.-% (ber. als C103) eingestellt wird. Optimale Ergebnisse werden bei Konzentrationen im Bereich von 0,001bis 0,035 Gew.-% (ber. als C103) erhalten.The best results are achieved if the content of chlorate or an accelerator having the same effect is set to concentrations below 0.05% by weight, preferably below 0.035% by weight (calculated as C10 3 ). Optimal results are obtained at concentrations in the range of 0.001 to 0.035% by weight (calculated as C10 3 ).

Bei der Bemessung des das Eisen(II) zu Eisen(III) oxidierenden Beschleunigers ist zu berücksichtigen, daß das Phosphatierbad z.B. in der Startphase noch keine Eisen(II)ionen enthält. Zu diesem Zeitpunkt ist daher eine Zugabe des Eisen(II) oxidierenden Beschleunigers nicht erforderlich. Auch ist es nicht erforderlich, diesen Beschleuniger ständig zu dosieren. Er kann durchaus auch mit den zur Badergänzung üblicherweise zugegebenen Chemikalien eingebracht werden.When dimensioning the accelerator that oxidizes iron (II) to iron (III), it must be taken into account that the phosphating bath, for example, does not yet contain any iron (II) ions. It is therefore not necessary to add the iron (II) oxidizing accelerator at this point. It is also not necessary to meter this accelerator continuously. He can also go to the bathroom supplement usually added chemicals are introduced.

Eine Weiterbildung des Verfahrens sieht vor, die Oberflächen mit einer Lösung in Berührung zu bringen, die zusätzlich Kalzium in Mengen von 0,01 bis 0,88 Gew.-%, vorzugsweise 0,15 bis 0,5 Gew.-%, enthält.A further development of the method provides for the surfaces to be brought into contact with a solution which additionally contains calcium in quantities of 0.01 to 0.88% by weight, preferably 0.15 to 0.5% by weight.

Dabei sollte das Gewichtsverhältnis Zn:Ca 1,5bLs 4 betragen. Beste Ergebnisse werden mit einem Verhältnis von 2,5 erzielt.The weight ratio Zn: Ca 1.5bLs 4 should be. Best results are achieved with a ratio of 2.5.

Schließlich kann die Phosphatierlösung noch weitere für Zinkphosphatierlösungen an sich übliche Zusätze, wie Kupfer, Kobalt, Nickel, einfaches oder komplexes Fluorid,enthalten. Bei der Fluoriddosierung ist zu beachten, daß kein Kalziumfluorid ausfällt. Magnesium kann das Kalzium teilweise oder ganz ersetzen. Schließlich kann - wie in der GB-PS 996 418 vorgeschlagen - der Phosphatierlösung Harnstoff zugesetzt werden.Finally, the phosphating solution can also contain other additives which are customary for zinc phosphating solutions, such as copper, cobalt, nickel, simple or complex fluoride. When dosing with fluoride, make sure that no calcium fluoride fails. Magnesium can partially or completely replace calcium. Finally, as suggested in GB-PS 996 418, urea can be added to the phosphating solution.

Die mit dem erfindungsgemäßen Verfahren in Berührung zu bringenden Oberflächen müssen frei von Rost und Zunder sein und sollten daher zunächst mit Mineralsäure, wie Salz- oder Schwefelsäure, gebeizt und anschließend mit Wasser gespült werden. Je nach Verunreinigung kann zur Reinigung der Oberflächen auch eine Entfettung oder andersartige Behandlung vorgenommen werden, beispielsweise mit einem organischen Lösungsmittel oder einem alkalischen Reiniger, gefolgt von einer Wasserspülung.The surfaces to be brought into contact with the method according to the invention must be free of rust and scale and should therefore first be pickled with mineral acid, such as hydrochloric or sulfuric acid, and then rinsed with water. Depending on the level of contamination, degreasing or other treatment can also be carried out to clean the surfaces, for example with an organic solvent or an alkaline cleaner, followed by a water rinse.

Die gereinigten Oberflächen können schließlich einer Aktivierungsbehandlung, z.B. durch Heißwasserspülung oder mit einer Titanorthophosphatdispersion, unterworfen werden.The cleaned surfaces can finally be subjected to an activation treatment, e.g. by hot water rinsing or with a titanium orthophosphate dispersion.

Das Tauchen oder Fluten der Oberflächen, das im Unterschied zum Spritzen eine Schlammbildung infolge Oxidation durch Luftsauerstoff weitgehend vermeidet, erfolgt gemäß einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens bei einer Temperatur von 35 bis 98 °C, vorzugsweise bei 55 bis 85 °C. Die Zeitdauer der Berührung zwischen Oberfläche und Phosphatierungslösung liegt vorzugsweise im Bereich von 5 bis 15 Minuten.Dipping or flooding the surfaces, which, unlike spraying, results in sludge formation due to oxidation Avoiding atmospheric oxygen to a large extent takes place according to a preferred embodiment of the method according to the invention at a temperature of 35 to 98 ° C, preferably 55 to 85 ° C. The period of contact between the surface and the phosphating solution is preferably in the range from 5 to 15 minutes.

Verteilhaft ist es, das Phosphatierbad mit einem Konzentratanzusetzen, das

Figure imgb0002
enthält und ein

  • Gewichtsverhältnis von Zn:P04 von 0,8 bis 4, vorzugsweise von 0,8 bis 1,4,
  • ein Gewichtsverhältnis von Zn:Ca von 1 bis 4, vorzugsweise von 2 bis 3,

und ein Verhältnis von Gesamtsäure zu Freier Säure von 5 bis 9, vorzugsweise 6 bis 8, aufweist.It is widespread to add the phosphating bath with a concentrate that
Figure imgb0002
 contains and a
  • Weight ratio of Zn: P0 4 from 0.8 to 4, preferably from 0.8 to 1.4,
  • a weight ratio of Zn: Ca from 1 to 4, preferably from 2 to 3,

and has a total acid to free acid ratio of 5 to 9, preferably 6 to 8.

Eine vorteilhafte Weiterbildung des erfindungsgemäßen Verfahrens besteht darin, die Oberflächen mit einer Lösung in Berührung zu bringen, die mit einem Konzentrat ergänzt wird, das

Figure imgb0003
enthält, in dem das

  • Gewichtsverhältnis Zn:P04 0,3 bis 0,6, vorzugsweise 0,3 bis 0,4,
  • das Gewichtsverhältnis Zn:Ca 2 bis 8, vorzugsweise 3 bis 6,

und das Verhältnis Gesamtsäure zu Freier Säure 3 bis 6, vorzugsweise 4 bis 5, beträgt.An advantageous development of the method according to the invention consists in bringing the surfaces into contact with a solution which is supplemented with a concentrate which
Figure imgb0003
 contains in which the
  • Weight ratio Zn: P0 4 0.3 to 0.6, preferably 0.3 to 0.4,
  • the weight ratio Zn: Ca 2 to 8, preferably 3 to 6,

and the ratio of total acid to free acid is 3 to 6, preferably 4 to 5.

Nach Ausbildung des Phosphatüberzuges kann mit kaltem Wasse

Figure imgb0004
und mit einer passiviererenden Nachspüllösung nach-
Figure imgb0005
Es Kann auch ein Scnmierittelüberzug auf
Figure imgb0006
Phosphatschicnt aufgebracht werden.After formation of the phosphate coating can be done with cold water
Figure imgb0004
and with a passivating rinse solution
Figure imgb0005
It can also have a lubricant coating on it
Figure imgb0006
Phosphatschicnt be applied.

Das erfindungsgemäße Verfahren hat sich insbesondere als

Figure imgb0007
für die spanlose Kaltumformung bewährt. Es ist
Figure imgb0008
auch mit Vorteil auf den übrigen Anwendungsgebieten
Figure imgb0009
Phosphatierung, z.B. für den Korrosionsschutz, zur Erleichterung der gleitenden Reibung und zur elektrischen Isolation einzusetzen.The method according to the invention has in particular proven to be
Figure imgb0007
Proven for non-cutting cold forming. It is
Figure imgb0008
also with advantage in the other areas of application
Figure imgb0009
Use phosphating, e.g. for corrosion protection, to facilitate sliding friction and for electrical insulation.

Die Erfindung wird anhand des Beispiels beispielsweise und näher erläutert.The invention is explained by way of example and in more detail.

Beispielexample

Es wurde eine Phosphatierungslösung aus einem Ansatzkonzentrat hergestellt, das

Figure imgb0010
enthielt und ein Verhältnis von Gesamtsäure zu Freier Säure von 7 aufwies. Die Verdünnung erfolgte im Verhältnis ein Teil Konzentrat, 20 Teile Wasser.A phosphating solution was prepared from a batch concentrate which
Figure imgb0010
 contained and had a ratio of total acid to free acid of 7. The dilution was carried out in the ratio of one part of concentrate to 20 parts of water.

In dem auf einer Temperatur von 70 °C gehaltenen Phosphatierbad wurde Draht im Tauchverfahren behandelt. Nach einer Kontaktzeit von 10 Minuten wurde der Draht entfernt, mit Wasser gespült, mit einem Schmiermittelüberzug versehen und auf übliche Art gezogen.Wire was immersed in the phosphating bath kept at a temperature of 70 ° C. After a contact time of 10 minutes, the wire was removed, rinsed with water, provided with a lubricant coating and pulled in the usual way.

Nach einem bestimmten Durchsatz wurde mit einem Ergänzungskonzentrat, das

Figure imgb0011
und enthielt und ein Verhältnis von Gesamtsäure zu Freier Säure von 4,6 aufwies, ergänzt.After a certain throughput was supplemented with a concentrate that
Figure imgb0011
 and contained and had a total acid to free acid ratio of 4.6.

Bei geeignetem Zusatz der Ergänzungslösung konnte das Phosphatierbad praktisch konstant bei Konzentrationen von

Figure imgb0012
Fell kleiner als 0,2 Gew.-% gehalten werden. Das Verhältnis Gesamtsäure zu Freier Säure lag bei 8,7.With a suitable addition of the supplementary solution, the phosphating bath could be kept practically constant at concentrations of
Figure imgb0012
 Fur smaller than 0.2 wt .-% are kept. The ratio of total acid to free acid was 8.7.

Das Verfahren konnte auf längere Zeit mit nur geringer Schlammbildung betrieben werden.The process could be operated for a long time with only a small amount of sludge.

Wurde hingegen zum Vergleich das Verfahren gemäß Beispiel 5 der GB-PS 1 555 529 betrieben, wurde zwar ebenfalls eine einwandfreie Phosphatschicht erhalten, jedoch war nach längerer Betriebsdauer der Chemikalienverbrauch etwa 40 % höher und das Gewicht des zu entfernenden Schlammes etwa 60 % größer.;If, on the other hand, the method according to Example 5 of GB-PS 1 555 529 was operated for comparison, a perfect phosphate layer was also obtained, but after a long period of operation the chemical consumption was about 40% higher and the weight of the sludge to be removed was about 60% greater .;

Claims (9)

1 Verfahren zur Herstellung von Phosphatüberzügen auf
Figure imgb0013
Figure imgb0014
Stahloberflächen im Tauch- oder Flutverfahren mit eine wäßrigen sauren Zinkphosphatlösung, dadurch gekennzeichnet, daß man die Oberflächen mit einer Lösung in
Figure imgb0015
bringt, die mindestens 0,3 Gew.-% Zn, minderten 0,3 Gew.-% PO, und mindestens 0,75 Gew.-% NO3 oder eines glsichwirkenden Eisen(II) nicht cxidierenden Beschleuni- gers enthält, in der das Gewichtsverhältnis Zn:P04 großer als 0,8 ist, das Verhältnis von Gesamtsäure zu Freier Säurmindestens 5 beträgt und in der man durch geeignete Bemessung von ClO3 oder einem gleichwirkenden Eisen(II) zu Eisen(III) oxidierenden Beschleuniger einen Eisen(II)-Gehalt von 0,05 bis 1 Gew.-% einstellt.1 Process for the preparation of phosphate coatings
Figure imgb0013
Figure imgb0014
Steel surfaces by immersion or flooding with an aqueous acidic zinc phosphate solution, characterized in that the surfaces with a solution in
Figure imgb0015
brings, which contains at least 0.3 wt .-% Zn, reduced 0.3 wt .-% PO, and at least 0.75 wt .-% NO 3 or a non-oxidizing accelerating iron (II) in which the weight ratio Zn: P0 4 is greater than 0.8, the ratio of total acid to free acid is at least 5 and in which, by suitable measurement of ClO 3 or a similarly acting iron (II) to iron (III) oxidizing accelerator, an iron (II ) Content of 0.05 to 1 wt .-%. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Oberflächen mit einer Lösung in Berührung bringt, die . maximal 2,2 Gew.-% Zn, max. 2,2 Gew.-% P04 und max. 5,5 Gew.-% N03 oder eines gleichwirkenden Beschleunigers enthält, in der das Gewichtsverhältnis Zn:PO4 kleiner als 4 ist und das Verhältnis von Gesamtsäure zu Freier Säure max. 30 beträgt.2. The method according to claim 1, characterized in that the surfaces are brought into contact with a solution which. maximum 2.2% by weight Zn, max. 2.2% by weight of P0 4 and max. 5.5 wt .-% N0 3 or an equivalent accelerator, in which the weight ratio Zn: PO 4 is less than 4 and the ratio of total acid to free acid max. 30 is. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Oberflächen mit einer Lösung in Berührung bringt, die 0,3 bis 1 Gew.-% Zn, 0,3 bis 1 Gew.-% P04 und 1 bis 3 Gew.-% NO3 oder eines gleichwirkenden Beschleunigers enthält, in der das Gewichtsverhältnis Zn:PO4 0,8 bis 2, insbesondere 0,8 bis 1,4, beträgt und die ein Verhältnis von Gesamtsäure zu Freier Säure von max. 15, insbesondere 7 bis 12, aufweist und in der man durch geeignete Bemessung von Chlorat oder einem gleichwirkenden Beschleuniger einen Eisen(II)-Gehalt von 0,08 bis 0,5, insbesondere bis 0,2 Gew.-%, einstellt.3. The method according to claim 1 or 2, characterized in that the surfaces are brought into contact with a solution containing 0.3 to 1% by weight of Zn, 0.3 to 1% by weight of P0 4 and 1 to 3 % By weight NO 3 or an accelerator having the same effect, in which the weight ratio Zn: PO 4 is 0.8 to 2, in particular 0.8 to 1.4, and which has a ratio of total acid to free acid of max. 15, in particular 7 to 12, and in which an iron (II) content of 0.08 to 0.5, in particular up to 0.2% by weight, is set by suitable dimensioning of chlorate or an accelerator having the same effect. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Oberflächen mit einer Lösung in Berührung bringt, die zusätzlich Kalzium in Mengen von 0,1 bis 0,88 Gew.-%, vorzugsweise 0,15 bis 0,5 Gew.-%, enthält.4. The method according to claim 1, 2 or 3, characterized in that the surfaces are brought into contact with a solution which additionally contains calcium in amounts of 0.1 to 0.88% by weight, preferably 0.15 to 0, 5% by weight. 5. Verfahren nach Anspruch 1, 2, 3 oder 4, dadurch gekennzeichnet, daß man die Oberflächen mit einer Lösung in Berührung bringt, die zusätzlich Kupfer, Kobald, Nickel, einfaches oder komplexes Fluorid enthält.5. The method according to claim 1, 2, 3 or 4, characterized in that the surfaces are brought into contact with a solution which additionally contains copper, cobalt, nickel, simple or complex fluoride. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Oberflächen mit der Lösung bei einer Temperatur von 35 bis 98 °C, vorzugsweise 55 bis 85 C, in Berührung bringt.6. The method according to one or more of claims 1 to 5, characterized in that the surfaces are brought into contact with the solution at a temperature of 35 to 98 ° C, preferably 55 to 85 ° C. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Oberflächen mit der Lösung während einer Zeitdauer von 5 bis 15 Minuten in Berührung bringt.7. The method according to one or more of claims 1 to 6, characterized in that the surfaces are brought into contact with the solution for a period of 5 to 15 minutes. 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Oberflächen mit einer Lösung in Berührung bringt, die mit einem Konzentrat ergänzt wird, das
Figure imgb0016
enthält, in dem das Gewichtsverhältnis Zn:PO4 0,3 bis 0,6, vorzugsw. 0,3 bis 0,4, das Gewichtsverhältnis Zn: Ca 2 bis 8, vorzugsweise 3 bis 6, und das Verhältnis Gesamtsäure zu Freier Säure 3 bis 6, vorzugsweise 4 bis 5, beträgt. 8. The method according to one or more of claims 1 to 7, characterized in that the surfaces are brought into contact with a solution which is supplemented with a concentrate which
Figure imgb0016
 contains in which the Weight ratio Zn: PO 4 0.3 to 0.6, preferably 0.3 to 0.4, the Zn: Ca weight ratio is 2 to 8, preferably 3 to 6, and the total acid to free acid ratio is 3 to 6, preferably 4 to 5. 9. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 8 zur Vorbereitung von Metalloberflächen für die Kaltverformung.9. Application of the method according to one or more of claims 1 to 8 for the preparation of metal surfaces for cold forming.
EP81200830A 1980-07-25 1981-07-21 Method for the production of phosphate coatings on iron and steel surfaces, and its use Expired EP0045110B1 (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0155547A1 (en) * 1984-03-01 1985-09-25 Gerhard Collardin GmbH Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature
EP0269138A1 (en) * 1986-10-25 1988-06-01 Metallgesellschaft Ag Process for producing phosphate coatings on metals
EP0271069A2 (en) * 1986-12-09 1988-06-15 Nippondenso Co., Ltd. Process for the phosphate chemical conversion treatment of a steel material
EP0287133A1 (en) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Phosphating treatment before electrophoretic dip painting
EP0363200A2 (en) * 1988-10-06 1990-04-11 Nippon Paint Co., Ltd. Improvement of zinc phosphate treatment for cold working
US4944813A (en) * 1988-01-14 1990-07-31 Gerhard Collardin Gmbh Process for phosphating metal surfaces
US4950339A (en) * 1988-02-03 1990-08-21 Metallgesellschaft Aktiengesellschaft Process of forming phosphate coatings on metals
EP0407015A1 (en) * 1989-05-15 1991-01-09 Nippon Paint Co., Ltd. Phosphate coated metal product, process for producing it, concentrate for use in the process and concentrate for replenishing the coating solution
US5039361A (en) * 1988-12-02 1991-08-13 Metallgesellschaft Aktiengesellschaft Process of phosphating metal surfaces
EP0613964A1 (en) * 1993-03-02 1994-09-07 Metallgesellschaft Aktiengesellschaft Process for facilitating cold forming
WO1998008999A1 (en) * 1996-08-28 1998-03-05 Metallgesellschaft Aktiengesellschaft Process and aqueous solution for phosphatising metallic surfaces
WO2004099468A1 (en) * 2003-05-06 2004-11-18 Chemetall Gmbh Method for coating metal bodies with a phosphating solution and phosphating solution
US8349092B2 (en) 2002-07-10 2013-01-08 Chemetall Gmbh Process for coating metallic surfaces

Families Citing this family (7)

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DE3244715A1 (en) * 1982-12-03 1984-06-07 Gerhard Collardin GmbH, 5000 Köln METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS
JPS6081850A (en) * 1983-10-11 1985-05-09 Nec Kansai Ltd Manufacture of semiconductor device
US5236565A (en) * 1987-04-11 1993-08-17 Metallgesellschaft Aktiengesellschaft Process of phosphating before electroimmersion painting
JPH01108754A (en) * 1987-10-21 1989-04-26 Toshiba Corp Lead frame for semiconductor device
DE3742634A1 (en) * 1987-12-16 1989-06-29 Collardin Gmbh Gerhard METHOD FOR THE COLLIGHTING OF PHOSPHATING BAEDERS AND DEVICE FOR THIS METHOD
US5954892A (en) * 1998-03-02 1999-09-21 Bulk Chemicals, Inc. Method and composition for producing zinc phosphate coatings on metal surfaces
CN101665936B (en) * 2009-09-27 2012-11-28 大连三达奥克化学股份有限公司 Normal-temperature phosphating agent for pre-processing before spray-coating of steel plate workpiece and preparation method thereof

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0155547A1 (en) * 1984-03-01 1985-09-25 Gerhard Collardin GmbH Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature
EP0269138A1 (en) * 1986-10-25 1988-06-01 Metallgesellschaft Ag Process for producing phosphate coatings on metals
EP0271069A2 (en) * 1986-12-09 1988-06-15 Nippondenso Co., Ltd. Process for the phosphate chemical conversion treatment of a steel material
EP0271069A3 (en) * 1986-12-09 1989-04-19 Nippondenso Co., Ltd. Process for the phosphate chemical conversion treatment of a steel material
EP0287133A1 (en) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Phosphating treatment before electrophoretic dip painting
US4944813A (en) * 1988-01-14 1990-07-31 Gerhard Collardin Gmbh Process for phosphating metal surfaces
EP0324395B1 (en) * 1988-01-14 1992-12-16 Gerhard Collardin Gmbh Process for phosphatizing metal surfaces
US4950339A (en) * 1988-02-03 1990-08-21 Metallgesellschaft Aktiengesellschaft Process of forming phosphate coatings on metals
EP0363200A3 (en) * 1988-10-06 1990-07-18 Nippon Paint Co., Ltd. Improvement of zinc phosphate treatment for cold working
EP0363200A2 (en) * 1988-10-06 1990-04-11 Nippon Paint Co., Ltd. Improvement of zinc phosphate treatment for cold working
US5039361A (en) * 1988-12-02 1991-08-13 Metallgesellschaft Aktiengesellschaft Process of phosphating metal surfaces
EP0407015A1 (en) * 1989-05-15 1991-01-09 Nippon Paint Co., Ltd. Phosphate coated metal product, process for producing it, concentrate for use in the process and concentrate for replenishing the coating solution
EP0613964A1 (en) * 1993-03-02 1994-09-07 Metallgesellschaft Aktiengesellschaft Process for facilitating cold forming
US5415701A (en) * 1993-03-02 1995-05-16 Metallgesellschaft Aktiengesellschaft Process for facilitating cold-working operations
CN1040779C (en) * 1993-03-02 1998-11-18 金属股份公司 Process for facilitating cold-working operation
WO1998008999A1 (en) * 1996-08-28 1998-03-05 Metallgesellschaft Aktiengesellschaft Process and aqueous solution for phosphatising metallic surfaces
CN1080325C (en) * 1996-08-28 2002-03-06 金属股份有限公司 Process and aqueous solution for phosphatising metallic surfaces
US8349092B2 (en) 2002-07-10 2013-01-08 Chemetall Gmbh Process for coating metallic surfaces
WO2004099468A1 (en) * 2003-05-06 2004-11-18 Chemetall Gmbh Method for coating metal bodies with a phosphating solution and phosphating solution

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EP0045110B1 (en) 1984-10-10
ATE9823T1 (en) 1984-10-15
PT73426B (en) 1982-08-09
PT73426A (en) 1981-08-01
IT1167480B (en) 1987-05-13
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GB2080835B (en) 1984-08-30

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