EP0711849A1 - Process for applying phosphate coatings - Google Patents
Process for applying phosphate coatings Download PDFInfo
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- EP0711849A1 EP0711849A1 EP95115909A EP95115909A EP0711849A1 EP 0711849 A1 EP0711849 A1 EP 0711849A1 EP 95115909 A EP95115909 A EP 95115909A EP 95115909 A EP95115909 A EP 95115909A EP 0711849 A1 EP0711849 A1 EP 0711849A1
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- ions
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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
- C23C22/368—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 magnesium cations
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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
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
Definitions
- the invention relates to a process for applying phosphate coatings to workpieces made of steel with the aid of phosphating solutions containing acidic, aqueous manganese, phosphate, nitrate and possibly iron (II) ions, and to the use of the process for the treatment of sliding friction Workpieces.
- Manganese phosphate coatings have proven themselves well for various applications, for example reducing the friction of metal surfaces sliding on one another or facilitating the cold forming of metals, because of their high mechanical resistance. With the initially common manganese phosphate solutions, however, relatively thick, coarsely crystalline layers were obtained, which are particularly disadvantageous when precision mechanical parts are to be treated. Numerous proposals have therefore been made with the aim of producing thin, fine-crystalline manganese phosphate coatings. For example, it is known to obtain a refinement of the phosphate layer by adding condensed phosphates.
- phosphating solutions based on manganese phosphate are generally used at high temperatures, so that owing to the considerable hydrolysis at high temperatures, the effectiveness of the condensed phosphates quickly decreases or the condensed phosphate must be replenished continuously.
- the German Auslegeschrift 1 109 484 describes another way to achieve fine-grained phosphate coatings. Thereafter, nitrate-containing phosphate solutions are used in which the amount of nitrate exceeds the amount of phosphate. The solutions should have a ratio of nitrate to phosphate of approximately (1.5 to 4.5): 1. However, it was found that in many cases the intended effect is not achieved.
- a phosphating solution based on manganese phosphate or manganese iron phosphate in which the concentrations with respect to manganese, iron (II), phosphate and nitrate ions are within certain limits, more free P2O5 in relation to the total P2O5 to supply than the phosphating equilibrium in the working phosphating solution corresponds.
- the above measure is said to have the advantage that a significant reduction in the sludge formed in the phosphating and a reduction in the chemicals required to produce a certain amount of coating is achieved (DE-B-22 13 781).
- nickel was considered an indispensable component of the phosphating solutions.
- the advantages of nickel are that the pickling attack on the base material is evened out and the resulting improvement in the adhesion of the phosphate layer obtained.
- the nickel ion content improves the optical appearance of the phosphate layer produced owing to a generally desired darkening.
- the nickel content in the phosphating solutions and of nickel or nickel compounds in the phosphate layers formed has disadvantages insofar as nickel and nickel compounds are from the point of view of Workplace hygiene and environmental protection are to be classified as questionable.
- the object of the invention is therefore to provide a process for applying phosphate coatings to workpieces made of steel with the aid of phosphating solutions containing acidic, aqueous manganese, phosphate, nitrate and possibly iron (II) ions, which has the disadvantages of the known, in particular does not have the abovementioned processes, in particular is nickel-free, but despite the absence of nickel leads to phosphate layers, the quality of which practically equates to that which is achieved with phosphating solutions containing nickel ions.
- the above-mentioned total number of points is determined by titrating 10 ml of the phosphating solution after dilution with water to about 50 ml using phenolphthalein as an indicator until the color changes from colorless to red.
- the number of ml 0.1 n sodium hydroxide solution used for this gives the total number of points.
- Other indicators suitable for titration are thymolphthalein and ortho-cresolphthalein.
- the electrical indication with a pH of 8.5 can also be used as an end point.
- the weight ratio Mn: Mg (5 to 50): 1 achieves a maximum layer weight with a minimum of pickling removal.
- a further advantageous embodiment of the invention provides for the workpieces to be brought into contact with a phosphating solution which additionally contains complexing carboxylic acid, such as citric acid or tartaric acid, in a concentration of 0.1 to 2.0 g / l.
- the complexing agent additive in particular prevents clouding of the phosphating solution.
- the workpieces come into contact with the phosphating solution preferably at a temperature in the range from 75 to 95 ° C.
- the workpieces can be brought into contact with the phosphating solution in any way, preferably the immersion treatment.
- the treatment time is generally 1 to 15 minutes.
- phosphate coatings with a layer weight of generally 5 to 25 g / m 2 are achieved.
- the phosphate coatings produced with the invention can be painted in a manner known per se or can be provided with plastic coatings. In conjunction with anti-corrosion oils, they serve to increase rust resistance.
- the main application of the method according to the invention is, however, in the treatment of workpieces that are exposed to sliding friction.
- Gear parts made of steel were first degreased with a strongly alkaline, aqueous cleaner in immersion, then rinsed with water, then rinsed in a slurry of finely divided manganese phosphate and finally phosphated in a phosphating solution at a temperature of 80 ° C. for a period of 10 min in immersion.
- the phosphating solution contained: 11.8 g / l manganese 0.5 g / l magnesium 0.1 g / l iron (II) 36 g / l phosphate (calculated as P2O5) 4.6 g / l nitrate and 0.36 g / l citrate (calculated as citric acid).
- the total score of the phosphating solution was 80, the score of free acid 11 points (measured with 60 g concentrate per 1 liter of water). To determine the total number of points, reference is made to the explanations above.
- 10 ml bath solution after dilution to approx. 50 ml with dist. Water, possibly with the addition of K3 (Co (CN) 6) or K4 (Fe (CN) 6) to remove interfering metal cations, using dimethyl yellow as an indicator with n / 10 NaOH until pink changes titrated for yellow.
- the ml n / 10 NaOH consumed give the free acid. They are often referred to as the Free Acid Score (FS).
- FS Free Acid Score
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
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- Chemical Treatment Of Metals (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Werkstücke aus Stahl mit Hilfe von sauren, wäßrigen Mangan-, Phosphat-, Nitrat- und ggf. Eisen(II)-Ionen enthaltenden Phosphatierungslösungen sowie die Anwendung des Verfahrens zur Behandlung von einer gleitenden Reibung ausgesetzten Werkstücken.The invention relates to a process for applying phosphate coatings to workpieces made of steel with the aid of phosphating solutions containing acidic, aqueous manganese, phosphate, nitrate and possibly iron (II) ions, and to the use of the process for the treatment of sliding friction Workpieces.
Für verschiedene Anwendungszwecke, z.B. die Verminderung der Reibung aufeinandergleitender Metallflächen oder die Erleichterung der Kaltumformung von Metallen, haben sich Manganphosphatüberzüge wegen ihrer hohen mechanischen Beständigkeit gut bewährt. Mit den anfänglich gebräuchlichen Manganphosphatlösungen erhielt man jedoch verhältnismäßig dicke, grobkristalline Schichten, die insbesondere dann nachteilig sind, wenn feinmechanische Teile behandelt werden sollen. Mit dem Ziel, dünne feinkristalline Manganphosphatüberzüge zu erzeugen, sind daher zahlreiche Vorschläge unterbreitet worden. So ist es beispielsweise bekannt, durch Zusatz von kondensierten Phosphaten eine Verfeinerung der Phosphatschicht zu erhalten. Phosphatierungslösungen auf Basis Manganphosphat werden jedoch im allgemeinen bei hohen Temperaturen eingesetzt, so daß infolge der bei hohen Temperaturen beträchtlichen Hydrolyse die Wirksamkeit der kondensierten Phosphate schnell nachläßt bzw. ständig kondensiertes Phosphat nachdosiert werden muß.Manganese phosphate coatings have proven themselves well for various applications, for example reducing the friction of metal surfaces sliding on one another or facilitating the cold forming of metals, because of their high mechanical resistance. With the initially common manganese phosphate solutions, however, relatively thick, coarsely crystalline layers were obtained, which are particularly disadvantageous when precision mechanical parts are to be treated. Numerous proposals have therefore been made with the aim of producing thin, fine-crystalline manganese phosphate coatings. For example, it is known to obtain a refinement of the phosphate layer by adding condensed phosphates. However, phosphating solutions based on manganese phosphate are generally used at high temperatures, so that owing to the considerable hydrolysis at high temperatures, the effectiveness of the condensed phosphates quickly decreases or the condensed phosphate must be replenished continuously.
Einen anderen Weg beschreibt die deutsche Auslegeschrift 1 109 484, um zu feinkörnigen Phosphatüberzügen zu gelangen. Danach werden nitrathaltige Phosphatlösungen eingesetzt, bei denen die Nitratmenge die Phosphatmenge übersteigt. Die Lösungen sollen ein Verhältnis von Nitrat zu Phosphat von etwa (1,5 bis 4,5) : 1 aufweisen. Es zeigte sich jedoch, daß in vielen Fällen die beabsichtigte Wirkung nicht erzielt wird.The German Auslegeschrift 1 109 484 describes another way to achieve fine-grained phosphate coatings. Thereafter, nitrate-containing phosphate solutions are used in which the amount of nitrate exceeds the amount of phosphate. The solutions should have a ratio of nitrate to phosphate of approximately (1.5 to 4.5): 1. However, it was found that in many cases the intended effect is not achieved.
Weiterhin ist ein Verfahren bekannt, bei dem gezielt mit einem überhöhten Anteil an freier Säure in der Phosphatierungslösung gearbeitet wird, um besonders dünne Schichten zu erzeugen (DE-C-12 46 356). Diese Schichten sind jedoch wegen ihres niedrigen Flächengewichtes nur für Spezialfälle praktisch anwendbar.Furthermore, a method is known in which an excessive proportion of free acid in the phosphating solution is specifically used in order to produce particularly thin layers (DE-C-12 46 356). However, due to their low basis weight, these layers are only practical for special cases.
Schließlich ist es bekannt, einer Phosphatierungslösung auf Basis Manganphosphat bzw. Mangan-Eisenphosphat, bei der die Konzentrationen hinsichtlich Mangan-, Eisen(II)-, Phosphat- und Nitrat-Ionen innerhalb bestimmter Grenzen liegen, mehr freies P₂O₅ im Verhältnis zum Gesamt-P₂O₅ zuzuführen als dem Phosphatierungsgleichgewicht in der arbeitenden Phosphatierungslösung entspricht. Durch die vorgenannte Maßnahme soll als Vorteil erzielt werden, daß eine deutliche Verminderung des bei der Phosphatierung gebildeten Schlammes und eine Herabsetzung der zur Erzeugung einer bestimmten Überzugsmenge erforderlichen Chemikalien erzielt wird (DE-B-22 13 781).Finally, it is known, a phosphating solution based on manganese phosphate or manganese iron phosphate, in which the concentrations with respect to manganese, iron (II), phosphate and nitrate ions are within certain limits, more free P₂O₅ in relation to the total P₂O₅ to supply than the phosphating equilibrium in the working phosphating solution corresponds. The above measure is said to have the advantage that a significant reduction in the sludge formed in the phosphating and a reduction in the chemicals required to produce a certain amount of coating is achieved (DE-B-22 13 781).
In der Praxis war den vorstehend referierten Verfahren gemeinsam, daß Nickel als unverzichtbarer Bestandteil der Phosphatierungslösungen galt. Die Vorteile von Nickel bestehen in einer Vergleichmäßigung des Beizangriffes auf das Grundmaterial und dadurch bedingt in einer Haftungsverbesserung der erhaltenen Phosphatschicht. Außerdem verbessert der Gehalt an Nickel-Ionen das optische Aussehen der erzeugten Phosphatschicht infolge einer im allgemeinen erwünschten Dunkelfärbung.In practice, the processes cited above had in common that nickel was considered an indispensable component of the phosphating solutions. The advantages of nickel are that the pickling attack on the base material is evened out and the resulting improvement in the adhesion of the phosphate layer obtained. In addition, the nickel ion content improves the optical appearance of the phosphate layer produced owing to a generally desired darkening.
Der Nickelgehalt in den Phosphatierungslösungen und von Nickel bzw. Nickelverbindungen in den gebildeten Phosphatschichten bringt jedoch insofern Nachteile, als Nickel und Nickelverbindungen aus Sicht der Arbeitsplatzhygiene und des Umweltschutzes als bedenklich einzustufen sind.However, the nickel content in the phosphating solutions and of nickel or nickel compounds in the phosphate layers formed has disadvantages insofar as nickel and nickel compounds are from the point of view of Workplace hygiene and environmental protection are to be classified as questionable.
Aufgabe der Erfindung ist es daher, ein Verfahren zum Aufbringen von Phosphatüberzügen auf Werkstücke aus Stahl mit Hilfe von sauren, wäßrigen Mangan-, Phosphat-, Nitrat- und ggf. Eisen(II)-Ionen enthaltenden Phosphatierungslösungen bereitzustellen, das die Nachteile der bekannten, insbesondere vorgenannten Verfahren nicht aufweist, insbesondere nickelfrei ist, jedoch trotz Nickelfreiheit zu Phosphatschichten führt, deren Qualität praktisch denen, die mit Nickel-Ionen enthaltenden Phosphatierungslösungen erzielt werden, gleichkommt.The object of the invention is therefore to provide a process for applying phosphate coatings to workpieces made of steel with the aid of phosphating solutions containing acidic, aqueous manganese, phosphate, nitrate and possibly iron (II) ions, which has the disadvantages of the known, in particular does not have the abovementioned processes, in particular is nickel-free, but despite the absence of nickel leads to phosphate layers, the quality of which practically equates to that which is achieved with phosphating solutions containing nickel ions.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung in der Weise ausgebildet wird, daß man die Werkstücke mit einer Lösung in Kontakt bringt, die nickelfrei ist,
2 bis 20 g/l Mangan-Ionen
0,2 bis 4 g/l Magnesium-Ionen
bis 12 g/l Eisen(II)-Ionen
5 bis 50 g/l Phosphat-Ionen (berechnet als P₂O₅) und
1 bis 20 g/l Nitrat-Ionen
enthält, eine Gesamtpunktezahl von 20 bis 150 aufweist und in der das Gewichtsverhältnis
Mn : Mg = (5 bis 50) : 1 beträgt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the workpieces are brought into contact with a solution which is nickel-free,
2 to 20 g / l manganese ions
0.2 to 4 g / l magnesium ions
up to 12 g / l iron (II) ions
5 to 50 g / l phosphate ions (calculated as P₂O₅) and
1 to 20 g / l nitrate ions
contains, has a total score of 20 to 150 and in which the weight ratio
Mn: Mg = (5 to 50): 1.
Die vorstehend genannte Gesamtpunktezahl wird ermittelt, indem 10 ml der Phosphatierungslösung nach Verdünnung mit Wasser auf etwa 50 ml unter Verwendung von Phenolphthalein als Indikator bis zum Farbumschlag von farblos nach rot titriert werden. Die Anzahl der hierfür verbrauchten ml 0,1 n Natronlauge ergeben die Gesamtpunktezahl. Andere für die Titration geeignete Indikatoren sind Thymolphthalein und ortho-Kresolphthalein. Ferner ist die elektrische Indikation mit einem pH-Wert von 8,5 als Endpunkt anwendbar.The above-mentioned total number of points is determined by titrating 10 ml of the phosphating solution after dilution with water to about 50 ml using phenolphthalein as an indicator until the color changes from colorless to red. The number of ml 0.1 n sodium hydroxide solution used for this gives the total number of points. Other indicators suitable for titration are thymolphthalein and ortho-cresolphthalein. The electrical indication with a pH of 8.5 can also be used as an end point.
Durch das Gewichtsverhältnis Mn : Mg = (5 bis 50) : 1 wird ein Maximum an Schichtgewicht bei einem Minimum an Beizabtrag erzielt.The weight ratio Mn: Mg = (5 to 50): 1 achieves a maximum layer weight with a minimum of pickling removal.
Eine weitere vorteilhafte Ausgestaltung der Erfindung sieht vor, die Werkstücke mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich komplexierend wirkende Carbonsäure, wie Zitronensäure oder Weinsäure, in einer Konzentration von 0,1 bis 2,0 g/l enthält. Der Komplexbildnerzusatz verhindert insbesondere eine Trübung der Phosphatierungslösung.
Der Kontakt der Werkstücke mit der Phosphatierungslösung erfolgt vorzugsweise bei einer Temperatur im Bereich von 75 bis 95°C.A further advantageous embodiment of the invention provides for the workpieces to be brought into contact with a phosphating solution which additionally contains complexing carboxylic acid, such as citric acid or tartaric acid, in a concentration of 0.1 to 2.0 g / l. The complexing agent additive in particular prevents clouding of the phosphating solution.
The workpieces come into contact with the phosphating solution preferably at a temperature in the range from 75 to 95 ° C.
Die Werkstücke können mit der Phosphatierungslösung in beliebiger Weise in Kontakt gebracht werden, bevorzugt ist die Tauchbehandlung. Als Behandlungsdauer sind im allgemeinen 1 bis 15 min angemessen.The workpieces can be brought into contact with the phosphating solution in any way, preferably the immersion treatment. The treatment time is generally 1 to 15 minutes.
In der Regel ist es erforderlich, die Werkstücke vor der Phosphatierung zu reinigen. Hierzu dienen saure, neutrale oder alkalische Reiniger. Im allgemeinen wird zwischen der Reinigung der Werkstücke und der Phosphatierung gründlich mit Wasser gespült. Insbesondere nach einer Behandlung mit Alkalien und Säuren sollten die Werkstücke in einer wäßrigen Aufschlämmung von feinverteiltem Manganphosphat vorgespült werden, um bei der anschließenden Phosphatierung die Ausbildung besonders gleichmäßiger feinkristalliner Schichten zu fördern. Der Effekt ist bei der Phosphatierung in Phosphatierungslösung, die neben Mangan- auch Eisen(II)-Ionen enthalten, besonders ausgeprägt.As a rule, it is necessary to clean the workpieces before phosphating. Acidic, neutral or alkaline cleaners are used for this. In general, thorough rinsing with water is carried out between the cleaning of the workpieces and the phosphating. Especially after treatment with alkalis and acids, the workpieces should be rinsed in an aqueous slurry of finely divided manganese phosphate in order to promote the formation of particularly uniform, fine crystalline layers during the subsequent phosphating. The effect is particularly pronounced when phosphating in a phosphating solution which contains iron (II) ions in addition to manganese.
Mit Hilfe des erfindungsgemäßen Verfahrens werden Phosphatüberzüge mit einem Schichtgewicht von im allgemeinen 5 bis 25 g/m² erzielt.With the aid of the method according to the invention, phosphate coatings with a layer weight of generally 5 to 25 g / m 2 are achieved.
Überraschenderweise hat sich gezeigt, daß der Einsatz von Magnesium-Ionen enthaltenden Phosphatierungslösungen entsprechend dem erfindungsgemäßen Verfahren nicht nur zu Phosphatschichten führt, die hinsichtlich ihrer Qualität den mit Nickel-Ionen enthaltenden Phosphatierungslösungen erzielten Phosphatschichten gleichkommen, sondern daß sich der Gehalt an Magnesium-Ionen verbrauchsmindernd hinsichtlich des gesamten Chemikalienverbrauchs auswirkt.Surprisingly, it has been shown that the use of phosphating solutions containing magnesium ions in accordance with the process according to the invention not only leads to phosphate layers which, in terms of their quality, are equivalent to the phosphate layers obtained with phosphating solutions containing nickel ions, but that the content of magnesium ions reduces consumption in terms of total chemical consumption.
Die mit der Erfindung erzeugten Phosphatüberzüge können in an sich bekannter Weise lackiert oder mit Kunststoffüberzügen versehen werden. In Verbindung mit Korrosionsschutzölen dienen sie zur Erhöhung der Rostbeständigkeit. Der Hauptanwendungsfall des erfindungsgemäßen Verfahrens liegt jedoch in der Behandlung von Werkstücken, die einer gleitenden Reibung ausgesetzt werden.The phosphate coatings produced with the invention can be painted in a manner known per se or can be provided with plastic coatings. In conjunction with anti-corrosion oils, they serve to increase rust resistance. The main application of the method according to the invention is, however, in the treatment of workpieces that are exposed to sliding friction.
Die Erfindung wird anhand des folgenden Beispiels näher und beispielsweise erläutert.The invention is explained in more detail and, for example, using the following example.
Getriebeteile aus Stahl wurden zunächst mit einem stark alkalischen, wäßrigen Reiniger im Tauchen entfettet, anschließend mit Wasser gespült, danach in einer Aufschlämmung von feinverteiltem Manganphosphat vorgespült und schließlich in einer Phosphatierungslösung einer Temperatur von 80°C für die Dauer von 10 min im Tauchen phosphatiert. Die Phosphatierungslösung enthielt:
11,8 g/l Mangan
0,5 g/l Magnesium
0,1 g/l Eisen (II)
36 g/l Phosphat (berechnet als P₂O₅)
4,6 g/l Nitrat und
0,36 g/l Citrat (berechnet als Zitronensäure).Gear parts made of steel were first degreased with a strongly alkaline, aqueous cleaner in immersion, then rinsed with water, then rinsed in a slurry of finely divided manganese phosphate and finally phosphated in a phosphating solution at a temperature of 80 ° C. for a period of 10 min in immersion. The phosphating solution contained:
11.8 g / l manganese
0.5 g / l magnesium
0.1 g / l iron (II)
36 g / l phosphate (calculated as P₂O₅)
4.6 g / l nitrate and
0.36 g / l citrate (calculated as citric acid).
Die Gesamtpunktezahl der Phosphatierungslösung betrug 80, die Punktezahl der Freien Säure 11 Punkte (gemessen mit 60 g Konzentrat pro 1 l Wasser). Zur Bestimmung der Gesamtpunktezahl wird auf die obigen Ausführungen verwiesen. Zur Bestimmung der Freien Säure werden 10 ml Badlösung nach Verdünnung auf ca. 50 ml mit dest. Wasser, ggf. unter Zusatz von K₃(Co(CN)₆) oder K₄(Fe(CN)₆) zwecks Beseitigung störender Metallkationen, unter Verwendung von Dimethylgelb als Indikator mit n/10 NaOH bis zum Umschlag von Rosa nach Gelb titriert. Die verbrauchten ml n/10 NaOH ergeben die Freie Säure. Sie werden vielfach auch als Punktezahl der Freien Säure bezeichnet (FS).
1 ml 0,1 n Natronlauge ^ 7,098 mg freies P₂O₅.The total score of the phosphating solution was 80, the score of free acid 11 points (measured with 60 g concentrate per 1 liter of water). To determine the total number of points, reference is made to the explanations above. To determine the free acid, 10 ml bath solution after dilution to approx. 50 ml with dist. Water, possibly with the addition of K₃ (Co (CN) ₆) or K₄ (Fe (CN) ₆) to remove interfering metal cations, using dimethyl yellow as an indicator with n / 10 NaOH until pink changes titrated for yellow. The ml n / 10 NaOH consumed give the free acid. They are often referred to as the Free Acid Score (FS).
1 ml 0.1 N sodium hydroxide solution ^ 7.098 mg free P₂O₅.
Zum Ansatz der Phosphatierungslösung diente ein Konzentrat, das 6,39 Gew.-% Mangan, 0,27 Gew.-% Magnesium, 0,05 Gew.-% Eisen(II), 19,8 Gew.-% Phosphat (berechnet als P₂O₅), 2,52 Gew.-% Nitrat und 0,197 Gew.-% Citrat (berechnet als Zitronensäure) enthielt. Im Anschluß an die Phosphatierbehandlung wurde erneut mit Wasser gespült und abschließend getrocknet. Es wurden feinkörnige, gleichmäßig deckende Phosphatüberzüge hoher Flächendichte von dunkler Farbe erhalten. Sie entsprachen in ihrer Qualität mindestens denen, die mit nickelhaltigen Phosphatierungslösungen erhalten werden. Das Schichtgewicht lag bei 10 g/m².A concentrate containing 6.39% by weight of manganese, 0.27% by weight of magnesium, 0.05% by weight of iron (II), 19.8% by weight of phosphate (calculated as P₂O₅), 2.52 wt .-% nitrate and 0.197 wt .-% citrate (calculated as citric acid) contained. Following the phosphating treatment, it was rinsed again with water and finally dried. Fine-grained, uniformly covering phosphate coatings of high surface density and dark color were obtained. Their quality corresponded at least to those obtained with phosphating solutions containing nickel. The layer weight was 10 g / m².
Im Zusammenwirken mit der üblichen Ölbehandlung besaßen die Getriebeteile hervorragende Einlaufeigenschaften.In combination with the usual oil treatment, the gear parts had excellent running-in properties.
Claims (5)
2 bis 20 g/l Mangan-Ionen
0,2 bis 4 g/l Magnesium-Ionen
bis 12 g/l Eisen(II)-Ionen
5 bis 50 g/l Phosphat-Ionen (ber. als P₂O₅) und
1 bis 20 g/l Nitrat-Ionen
enthält, eine Gesamtpunktezahl von 20 bis 150 aufweist und in der das Gewichtsverhältnis Mn : Mg = (5 bis 50) : 1 beträgt.Process for applying phosphate coatings to steel workpieces with the aid of phosphating solutions containing acidic, aqueous manganese, phosphate, nitrate and possibly iron (II) ions, characterized in that the workpieces are brought into contact with a solution which is nickel free,
2 to 20 g / l manganese ions
0.2 to 4 g / l magnesium ions
up to 12 g / l iron (II) ions
5 to 50 g / l phosphate ions (calculated as P₂O₅) and
1 to 20 g / l nitrate ions
contains, has a total score of 20 to 150 and in which the weight ratio Mn: Mg = (5 to 50): 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4440300 | 1994-11-11 | ||
| DE4440300A DE4440300A1 (en) | 1994-11-11 | 1994-11-11 | Process for applying phosphate coatings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0711849A1 true EP0711849A1 (en) | 1996-05-15 |
| EP0711849B1 EP0711849B1 (en) | 1998-01-14 |
Family
ID=6533058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95115909A Expired - Lifetime EP0711849B1 (en) | 1994-11-11 | 1995-10-10 | Process for applying phosphate coatings |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0711849B1 (en) |
| AT (1) | ATE162232T1 (en) |
| DE (2) | DE4440300A1 (en) |
| DK (1) | DK0711849T3 (en) |
| ES (1) | ES2112593T3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0904425A4 (en) * | 1996-02-14 | 1999-04-21 | ||
| WO2001023638A1 (en) * | 1999-09-30 | 2001-04-05 | Chemetall Gmbh | Method for applying manganese phosphate layers |
| WO2001034874A1 (en) * | 1999-11-05 | 2001-05-17 | Nippon Steel Corporation | Galvanized steel for use in vehicle body |
| US9506151B2 (en) | 1999-09-30 | 2016-11-29 | Chemetall Gmbh | Method for applying manganese phosphate layers |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094196B (en) * | 2011-03-24 | 2012-07-04 | 上海奉贤钢管厂 | Process for parkerising internal surface of long thin steel tube with manganese phosphate |
| DE102017207594A1 (en) | 2017-05-05 | 2018-11-08 | Federal-Mogul Nürnberg GmbH | Thermal insulation of a steel piston by means of a manganese phosphate and a polysilazane layer |
| CN109609942B (en) * | 2018-12-28 | 2020-12-04 | 湖南金化科技集团有限公司 | Manganese-magnesium phosphating solution |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1109484B (en) | 1956-02-29 | 1961-06-22 | American Chem Paint Co | Manganese phosphate coatings |
| DE1109978B (en) * | 1957-04-05 | 1961-06-29 | Arthur Uecker K G Dr | Process to prevent sludge formation in the production of oxide-phosphate layers |
| DE1246356B (en) | 1963-07-30 | 1967-08-03 | Metallgesellschaft Ag | Process for the production of manganese phosphate coatings on iron and steel |
| DE2213781A1 (en) | 1972-03-22 | 1973-09-27 | Metallgesellschaft Ag | METHOD OF PHOSPHATING STEEL |
| DE2213718A1 (en) * | 1972-03-21 | 1973-10-04 | Dreefs E Gmbh | SWITCHING DEVICE |
| EP0015020A1 (en) * | 1979-02-14 | 1980-09-03 | Metallgesellschaft Ag | Process for the surface treatment of metals and its use for the treatment of aluminium surfaces |
| US4681641A (en) * | 1982-07-12 | 1987-07-21 | Ford Motor Company | Alkaline resistant phosphate conversion coatings |
| FR2601698A1 (en) * | 1986-07-17 | 1988-01-22 | Solypro Nouvelle Exploit | Phosphating bath and process |
| WO1990015889A1 (en) * | 1989-06-21 | 1990-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing zinc phosphate coatings containing manganese and magnesium |
| EP0459541A1 (en) * | 1990-04-27 | 1991-12-04 | METALLGESELLSCHAFT Aktiengesellschaft | Process for phosphating metal surfaces |
| WO1994014999A1 (en) * | 1992-12-22 | 1994-07-07 | Henkel Corporation | Substantially nickel-free phosphate conversion coating composition and process |
-
1994
- 1994-11-11 DE DE4440300A patent/DE4440300A1/en not_active Withdrawn
-
1995
- 1995-10-10 DE DE59501279T patent/DE59501279D1/en not_active Expired - Lifetime
- 1995-10-10 AT AT95115909T patent/ATE162232T1/en active
- 1995-10-10 DK DK95115909.4T patent/DK0711849T3/en active
- 1995-10-10 ES ES95115909T patent/ES2112593T3/en not_active Expired - Lifetime
- 1995-10-10 EP EP95115909A patent/EP0711849B1/en not_active Expired - Lifetime
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1109484B (en) | 1956-02-29 | 1961-06-22 | American Chem Paint Co | Manganese phosphate coatings |
| DE1109978B (en) * | 1957-04-05 | 1961-06-29 | Arthur Uecker K G Dr | Process to prevent sludge formation in the production of oxide-phosphate layers |
| DE1246356B (en) | 1963-07-30 | 1967-08-03 | Metallgesellschaft Ag | Process for the production of manganese phosphate coatings on iron and steel |
| US3450578A (en) * | 1963-07-30 | 1969-06-17 | Hooker Chemical Corp | Process and composition for the production of protective coatings |
| DE2213718A1 (en) * | 1972-03-21 | 1973-10-04 | Dreefs E Gmbh | SWITCHING DEVICE |
| FR2176647A1 (en) * | 1972-03-22 | 1973-11-02 | Parker Ste Continentale | |
| DE2213781A1 (en) | 1972-03-22 | 1973-09-27 | Metallgesellschaft Ag | METHOD OF PHOSPHATING STEEL |
| EP0015020A1 (en) * | 1979-02-14 | 1980-09-03 | Metallgesellschaft Ag | Process for the surface treatment of metals and its use for the treatment of aluminium surfaces |
| US4681641A (en) * | 1982-07-12 | 1987-07-21 | Ford Motor Company | Alkaline resistant phosphate conversion coatings |
| FR2601698A1 (en) * | 1986-07-17 | 1988-01-22 | Solypro Nouvelle Exploit | Phosphating bath and process |
| WO1990015889A1 (en) * | 1989-06-21 | 1990-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing zinc phosphate coatings containing manganese and magnesium |
| EP0459541A1 (en) * | 1990-04-27 | 1991-12-04 | METALLGESELLSCHAFT Aktiengesellschaft | Process for phosphating metal surfaces |
| WO1994014999A1 (en) * | 1992-12-22 | 1994-07-07 | Henkel Corporation | Substantially nickel-free phosphate conversion coating composition and process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0904425A4 (en) * | 1996-02-14 | 1999-04-21 | ||
| WO2001023638A1 (en) * | 1999-09-30 | 2001-04-05 | Chemetall Gmbh | Method for applying manganese phosphate layers |
| US9506151B2 (en) | 1999-09-30 | 2016-11-29 | Chemetall Gmbh | Method for applying manganese phosphate layers |
| WO2001034874A1 (en) * | 1999-11-05 | 2001-05-17 | Nippon Steel Corporation | Galvanized steel for use in vehicle body |
| US6623868B1 (en) | 1999-11-05 | 2003-09-23 | Nippon Steel Corporation | Galvanized steel for use in vehicle body |
| AU767115B2 (en) * | 1999-11-05 | 2003-10-30 | Nippon Steel Corporation | Galvanized steel for use in vehicle body |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59501279D1 (en) | 1998-02-19 |
| DE4440300A1 (en) | 1996-05-15 |
| ES2112593T3 (en) | 1998-04-01 |
| DK0711849T3 (en) | 1998-03-16 |
| ATE162232T1 (en) | 1998-01-15 |
| EP0711849B1 (en) | 1998-01-14 |
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