EP0059994A1 - Process for the production of phosphate coatings on metal surfaces - Google Patents
Process for the production of phosphate coatings on metal surfaces Download PDFInfo
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- EP0059994A1 EP0059994A1 EP82200190A EP82200190A EP0059994A1 EP 0059994 A1 EP0059994 A1 EP 0059994A1 EP 82200190 A EP82200190 A EP 82200190A EP 82200190 A EP82200190 A EP 82200190A EP 0059994 A1 EP0059994 A1 EP 0059994A1
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- metal surfaces
- phosphating bath
- weight ratio
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- phosphating
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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
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
Definitions
- aqueous acidic zinc phosphate solutions which contain chlorate as an accelerator and additionally nitrate to apply phosphate coatings to metal surfaces by immersion or flooding.
- chlorate-containing zinc phosphate solutions a weight ratio of P 2 O 5 : Z n in the range of approximately 1: (0.2 to 0.7) is usually observed (cf. for example DE-OS 21 06 626).
- calcium ions in such solutions in order to refine the phosphate layer (cf. for example DE-PS 10 96 152). However, this extends the treatment time until a closed phosphate layer is formed on the metal surfaces.
- the object of the invention is to further improve the known method, in particular the aforementioned method, so that its use leads to phosphate layers which, in particular with regard to their thickness and intergrowth, meet the highest requirements.
- Phosphating baths which only contain chlorate as accelerators can be used in the process according to the invention. In this case, its content must be at least 1.0 g / l (calculated as C10 3 ). If the phosphating bath also contains nitrate ions, the sum of chlorate and nitrate ions must be at least 1.0 g / 1. The nitrate content is determined as the oxidation equivalent based on chlorate.
- a phosphating bath is preferably used which contains up to 5 g / 1 chlorate, in particular 0.2 to 2 g / 1 chlorate.
- a further preferred embodiment of the invention consists in bringing the metal surfaces into contact with a phosphating bath which contains 5 to 20 g / 1 sulfate ions. This generally achieves the layer thickening effect and the excellent anchoring of the phosphate layer to a sufficient extent.
- Concentrates are expediently used to prepare and supplement the phosphating bath used in the procedure according to the invention. It is advantageous to design them in such a way that - apart from the sulfate content - they contain as many components as possible. It is advisable to add the sulfate separately.
- the phosphating bath should preferably contain 5 to 1000 mg / 1 Ni and / or 1 to 50 mg / 1 Cu ions.
- the workpieces to be treated must be free of rust and scale.
- a possible course of treatment is, for example: degreasing with organic solvents or alkaline cleaners (the latter is then rinsed with water), pickling in mineral acids, such as HC1 or H 2 S0 4 , to remove scale and rust, rinsing with cold water.
- the workpieces can then be treated in the process according to the invention at temperatures between 35 and 98 ° C and a bath number of at least 20 5 to 15 minutes in immersion or flooding.
- the phosphating bath is supplemented with the supplementary concentrate mentioned.
- the surface of the workpieces can be activated by pre-rinsing with hot water or with activating titanium orthophosphate dispersions. After phosphating, the workpieces are rinsed with cold water and can then ach Whyillonen with passivating N or in cold formed parts with lubricants and optionally lubricant carrier salts, such as borax or lime-treated.
- lubricant carrier salts such as borax or lime-treated.
- the method according to the invention has proven particularly useful as a preparation for non-cutting cold forming. However, it is also advantageous in the other fields of application of phosphating, e.g. Use corrosion protection, to facilitate sliding friction.
- the phosphating baths had the following composition:
- the phosphate layers produced using baths containing sulfate ions are of considerably greater thickness.
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- Chemical Treatment Of Metals (AREA)
Abstract
Bei der Herstellung von Phosphatüberzügen auf Metalloberflächen, insbesondere Eisen und Stahl, bei 35 bis 98°C im Tauch- oder Flutverfahren mit einer Chlorat und gegebenenfalls Nitrat enthaltenden wäßrigen, sauren Zinkphosphatlösung bringt man die Metalloberflächen zwecks Erzeugung dicker und fest verwachsener Phosphatschichten mit einem Phosphatierungsbad in Berührung, in dem das Gewichtsverhältnis von P2O5 : Zn : ClO3 = 1 : (0,5 bis 4;0): (0,01 bis 1,0) beträgt und das zusätzlich 1 bis 50 g/l, vorzugsweise 5 bis 20 g/l, Sulfationen enthält. Zweckmäßigerweise weist das Phosphatierungsbad einen Chloratgehalt bis 5 g/l, vorzugsweise 0,2 bis 2 g/l, und ein Gewichtsverhältnis von P2O5 : NO3 = 1 : (0,2 bis 6) auf.In the production of phosphate coatings on metal surfaces, in particular iron and steel, at 35 to 98 ° C by immersion or flooding with an aqueous, acidic zinc phosphate solution containing chlorate and optionally nitrate, the metal surfaces are brought in with a phosphating bath in order to produce thick and firmly overgrown phosphate layers Touch in which the weight ratio of P2O5: Zn: ClO3 = 1: (0.5 to 4; 0): (0.01 to 1.0) and additionally 1 to 50 g / l, preferably 5 to 20 g / l, contains sulfate ions. The phosphating bath expediently has a chlorate content of up to 5 g / l, preferably 0.2 to 2 g / l, and a weight ratio of P2O5: NO3 = 1: (0.2 to 6).
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Phosphatüberzügen auf Metalloberflächen, insbesondere Eisen und Stahl, bei 35 bis 98°C im Tauch- oder Flutverfahren mit einer als Beschleuniger Chlorat und gegebenenfalls Nitrat enthaltenden wäßrigen, sauren Zinkphosphatlösung, die mindestens 6 g/1 Zink, mindestens 5 g/1 P205, mindestens 1,0 g/1 Beschleuniger (berechnet als C103) enthält, eine Gesamtsäurepunktzahl von mindestens 20 aufweist und in der das Gewichtsverhältnis von freiem P205 : Gesamt-P2O5 = (0.,2 bis 0,6) : 1 beträgt.The invention relates to a process for the production of phosphate coatings on metal surfaces, in particular iron and steel, at 35 to 98 ° C. in the immersion or flooding process with an aqueous acidic zinc phosphate solution containing chlorate and optionally nitrate, which contains at least 6 g / 1 zinc, contains at least 5 g / 1 P205, at least 1.0 g / 1 accelerator (calculated as C10 3 ), has a total acid number of at least 20 and in which the weight ratio of free P 2 0 5: total P 2 O 5 = (0 ., 2 to 0.6): 1 is.
Es ist bekannt, zum Aufbringen von Phosphatüberzügen auf Metalloberflächen im Tauch- oder Flutverfahren wäßrige saure Zinkphosphatlösungen, die Chlorat als Beschleuniger und zusätzlich Nitrat enthalten, zu verwenden. Bei chlorathaltigen Zinkphosphatlösungen wird üblicherweise ein Gewichtsverhältnis von P2O5 : Zn im Bereich von etwa 1 : (0,2 bis 0,7) eingehalten (vgl. z.B. DE-OS 21 06 626). Es ist auch bekannt, in derartigen Lösungen zusätzlich Kalziumionen mitzuverwenden,_ um die Phosphatschicht zu verfeinern (vgl. z.B. DE-PS 10 96 152). Die Behandlungszeit bis zur Ausbildung einer geschlossenen Phosphatschicht auf den Metalloberflächen wird hierdurch jedoch verlängert.It is known to use aqueous acidic zinc phosphate solutions which contain chlorate as an accelerator and additionally nitrate to apply phosphate coatings to metal surfaces by immersion or flooding. In the case of chlorate-containing zinc phosphate solutions, a weight ratio of P 2 O 5 : Z n in the range of approximately 1: (0.2 to 0.7) is usually observed (cf. for example DE-OS 21 06 626). It is also known to additionally use calcium ions in such solutions in order to refine the phosphate layer (cf. for example DE-PS 10 96 152). However, this extends the treatment time until a closed phosphate layer is formed on the metal surfaces.
Insbesondere für die Vorbereitung von Werkstücken für eine anschließende Kaltumformung sind die auf diese Weise erhaltenen Schichten wegen ihrer zu geringen Dicke nicht immer zufriedenstellend.In particular for the preparation of workpieces for subsequent cold forming, the layers obtained in this way are not always satisfactory because of their too small thickness.
Um diesen Nachteil zu vermeiden, wurden Lösungen zur Herstellung von Phosphatüberzügen auf Metalloberflächen, insbesondere Eisen und Stahl, bekannt, die bei 35 bis 98oC im Tauch- oder Flutverfahren angewendet werden und saures Zinkphosphat, Chlorat und Nitrat mit einem Gewichtsverhältnis von P2O5 : Zn = 1 : (0,8 bis 4,0) enthalten (DE-OS 25 40 685). Bei Einsatz derartiger Phosphatierungsbäder wird eine Phosphatschicht mit einer Kristallstruktur erhalten, die etwas weicher als üblich ist, wodurch die Aufnahmefähigkeit der Schicht für Schmiermittel, zum Beispiel bei der nachfolgenden Behandlung der phosphatierten Werkstücke in einer wäßrigen Seifenlösung, erhöht wird.To avoid this drawback, solutions have been known for the production of phosphate coatings on metal surfaces, particularly iron and steel, that are applied at 35 to 98 o C in the dipping or flow-coating method and acidic zinc phosphate, chlorate and nitrate in a weight ratio of P 2 O 5 : Zn = 1: (0.8 to 4.0) included (DE-OS 25 40 685). When such phosphating baths are used, a phosphate layer with a crystal structure is obtained which is somewhat softer than usual, which increases the absorption capacity of the layer for lubricants, for example during the subsequent treatment of the phosphated workpieces in an aqueous soap solution.
Besonders gute Ergebnisse wurden erhalten, wenn ein Phosphatierungsbad zum Einsatz kam, das mindestens 6 g/1 Zink, min- destens 5 g/1 P2O5, mindestens 1 g/l ClO3 und mindestens 8 g/1 N03 enthielt, eine Gesamtsäurepunktzahl von 20 bis 80 aufwies und in dem das Gewichtsverhältnis von P2O5 : Zn : NO3 : ClO3 = 1 : (1,5 bis 4,0) : (2,0 bis 6,0) : (0,0'3 bis 2,0) sowie von freiem P2O5 : Gesamt-P2O5 = (0,2 bis 0,6) : 1 betrug und das Bad ergänzt wurde mit einem Gewichtsverhältnis von P2O5 : Zn : NO3 : ClO3 = 1 : (0,40 bis 0,80) : (0,10 bis 0,60) : (0,15 bis 0,60) sowie von freiem P2O5 : Gesamt-P2O5 = (0,20 bis 0,70) : 1.Particularly good results were obtained when a phosphating bath was used which contained at least 6 g / 1 zinc, at least 5 g / 1 P 2 O 5 , at least 1 g / l ClO 3 and at least 8 g / 1 NO 3 . had a total acid score of 20 to 80 and in which the weight ratio of P 2 O 5 : Zn: NO 3: ClO 3 = 1: (1.5 to 4.0): (2.0 to 6.0): (0 , 0'3 to 2.0) and of free P 2 O 5 : total P 2 O 5 = (0.2 to 0.6): 1 and the bath was supplemented with a weight ratio of P 2 O 5 : Zn: NO 3 : ClO 3 = 1: (0.40 to 0.80): (0.10 to 0.60): (0.15 to 0.60) and from free P 2 O 5 : total P 2 O 5 = (0.20 to 0.70): 1.
Obgleich das zuletzt genannte Verfahren erhebliche Vorzüge aufweist, werden gelegentlich - insbesondere hinsichtlich Dicke und VBerwachsung der Phosphatschicht - Anforderungen gestellt, die auch dieses Verfahren nicht erfüllen kann.Although the last-mentioned method has considerable advantages, there are occasionally requirements, particularly with regard to the thickness and growth of the phosphate layer, which this method cannot meet either.
Aufgabe der Erfindung ist es, die bekannten, insbesondere das vorstehend genannte Verfahren weiter zu verbessern, so daß dessen Anwendung zu Phosphatschichten führt, die insbesondere hinsichtlich ihrer Dicke und Verwachsung höchsten Anforderungen genügen.The object of the invention is to further improve the known method, in particular the aforementioned method, so that its use leads to phosphate layers which, in particular with regard to their thickness and intergrowth, meet the highest requirements.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen mit einem Phosphatierungsbad in Berührung bringt, in dem das Gewichtsverhältnis von P205: Zn : C103 = 1 : (0,5 bis 4,0) : (0,01 bis 1,0) beträgt und das zusätzlich 1 bis 50 g/1 Sulfationen enthält.The object is achieved by designing the method of the type mentioned according to the invention in such a way that the metal surfaces are brought into contact with a phosphating bath in which the weight ratio of P205: Zn: C10 3 = 1: (0.5 to 4 , 0): (0.01 to 1.0) and which additionally contains 1 to 50 g / 1 sulfate ions.
Überraschenderweise.bewirkt der Zusatz von Sulfationen innerhalb des speziellen Phosphatierungsverfahrens eine beträchtliche Schichtverdickung, die in der Größenordnung von etwa 50 % liegen kann. Zudem wird eine optimale, nicht vorhersehbare Verankerung der Phosphatschicht auf der Metalloberfläche festgestellt.Surprisingly, the addition of sulfate ions within the special phosphating process causes a considerable layer thickening, which can be of the order of about 50%. In addition, an optimal, unforeseeable anchoring of the phosphate layer on the metal surface is determined.
Innerhalb des erfindungsgemäßen Verfahrens können Phosphatierungsbäder zum Einsatz kommen, die als Beschleuniger lediglich Chlorat enthalten. In diesem Fall muß dessen Gehalt mindestens 1,0 g/l (berechnet als C103) betragen. Enthält das Phosphatierungsbad zusätzlich Nitrationen, dann muß die Summe an Chlorat- und Nitrationen mindestens 1,0 g/1 sein. Hierbei wird.der Nitratgehalt als Oxidationsäquivalent bezogen auf Chlorat ermittelt.Phosphating baths which only contain chlorate as accelerators can be used in the process according to the invention. In this case, its content must be at least 1.0 g / l (calculated as C10 3 ). If the phosphating bath also contains nitrate ions, the sum of chlorate and nitrate ions must be at least 1.0 g / 1. The nitrate content is determined as the oxidation equivalent based on chlorate.
Vorzugsweise wird mit einem Phosphatierungsbad gearbeitet, das bis 5 g/1 Chlorat, insbesondere 0,2 bis 2 g/1 Chlorat, enthält.A phosphating bath is preferably used which contains up to 5 g / 1 chlorate, in particular 0.2 to 2 g / 1 chlorate.
Eine weitere bevorzugte Ausgestaltung der Erfindung besteht darin, die Metalloberflächen mit einem Phosphatierungsbad in Berührung zu bringen, das 5 bis 20 g/1 Sulfationen enthält. Hierdurch wird im allgemeinen der schichtverdickende Effekt und die hervorragende Verankerung der Phosphatschicht in ausreichendem Maße erzielt.A further preferred embodiment of the invention consists in bringing the metal surfaces into contact with a phosphating bath which contains 5 to 20 g / 1 sulfate ions. This generally achieves the layer thickening effect and the excellent anchoring of the phosphate layer to a sufficient extent.
Eine weitere bevorzugte Ausgestaltung des erfindungsgemäßen Verfahrens besteht darin, die Metalloberflächen mit einem Phosphatierungsbad in Berührung zu bringen, in dem das Gewichtsverhältnis von P205 : N03 = 1 : (0,2 bis 6) beträgt.Another preferred embodiment of the method according to the invention is to bring the metal surfaces into contact with a phosphating bath in which the weight ratio of P 2 0 5: N0 3 = 1: (0.2 to 6).
Zum Ansatz und zur Ergänzung des bei der erfindungsgemäßen Arbeitsweise angewendeten Phosphatierungsbades werden zweckmäßig Konzentrate benutzt. Es ist von Vorteil, diese so zu konzipieren, daß sie - vom Sulfatanteil abgesehen - möglichst alle benötigten Komponenten enthalten. Es empfiehlt sich, das Sulfat separat zuzugeben.Concentrates are expediently used to prepare and supplement the phosphating bath used in the procedure according to the invention. It is advantageous to design them in such a way that - apart from the sulfate content - they contain as many components as possible. It is advisable to add the sulfate separately.
Eine weitere vorteilhafte Ausgestaltung der Erfindung besteht daher darin, die Metalloberflächen mit einem Phosphatierungsbad in Berührung zu bringen, das entsprechend einem Gewichtsverhältnis von P205: Zn : NO3 : ClO3 = 1 : (0,36 bis 0,80) : (0,10 bis 0,60) : (0,15 bis 0,60) sowie von freiem P2O5 ': Gesamt-P2O5 = (0,20 bis 0,70) : 1 ergänzt wird.A further advantageous embodiment of the invention therefore consists in bringing the metal surfaces into contact with a phosphating bath which corresponds to a weight ratio of P 2 0 5: Z n : NO3: ClO 3 = 1: (0.36 to 0.80): (0.10 to 0.60): (0.15 to 0.60) and of free P 2 O 5 ': total P 2 O 5 = (0.20 to 0.70): 1 is added.
Falls erwünscht, können im Phosphatierungsbad auch weitere übliche Zusätze, wie z.B. Kupfer, Nickel, Cobalt oder auch einfaches und komplexes Fluorid, verwendet werden. Hinsichtlich Fluoridzusatz ist bei Ca-haltigen Bädern jedoch darauf zu achten, daß das Löslichkeitsprodukt von CaF2 nicht überschritten werden darf.If desired, other conventional additives, such as copper, nickel, cobalt or simple and complex fluoride, can also be used in the phosphating bath. With regard to the addition of fluoride, care must be taken with baths containing Ca that the solubility product of CaF 2 must not be exceeded.
Vorzugsweise sollte das Phosphatierungsbad 5 bis 1000 mg/1 Ni- und/oder 1 bis 50 mg/1 Cu-Ionen enthalten.The phosphating bath should preferably contain 5 to 1000 mg / 1 Ni and / or 1 to 50 mg / 1 Cu ions.
Die zu behandelnden Werkstücke müssen rost- und zunderfrei sein. Ein möglicher Behandlungsgang ist zum Beispiel: Entfetten mit organischen Lösungsmitteln oder alkalischen Reinigern (letzterenfalls wird anschließend mit Wasser gespült), Beizen in Mineralsäuren, wie z.B. HC1 oder H2S04, zur Entfernung von Zunder und Rost, Spülen mit kaltem Wasser.The workpieces to be treated must be free of rust and scale. A possible course of treatment is, for example: degreasing with organic solvents or alkaline cleaners (the latter is then rinsed with water), pickling in mineral acids, such as HC1 or H 2 S0 4 , to remove scale and rust, rinsing with cold water.
Die Werkstücke können dann nach dem erfindungsgemäßen Verfahren bei Temperaturen zwischen 35 und 98°C und einer Badpunktezahl von mindestens 20 5 bis 15 Minuten im Tauchen oder Fluten behandelt werden. Zur Aufrechterhaltung der Badpunktezahl wird das Phosphatierungsbad mit dem genannten Ergänzungskonzentrat ergänzt.The workpieces can then be treated in the process according to the invention at temperatures between 35 and 98 ° C and a bath number of at least 20 5 to 15 minutes in immersion or flooding. To maintain the number of bath points, the phosphating bath is supplemented with the supplementary concentrate mentioned.
Vor der phosphatierenden Behandlung kann die Oberfläche der Werkstücke durch eine Vorspülung mit heißem Wasser oder mit aktivierenden Titanorthophosphatdispersionen aktiviert werden. Nach der Phosphatierung werden die Werkstücke mit kaltem Wasser gespült und können anschließend mit passivierenden Nachspüllösungen oder bei Kaltumformteilen mit Schmiermitteln und gegebenenfalls Schmiermittelträgersalzen, wie Borax oder Kalk, nachbehandelt werden.Before the phosphating treatment, the surface of the workpieces can be activated by pre-rinsing with hot water or with activating titanium orthophosphate dispersions. After phosphating, the workpieces are rinsed with cold water and can then achspüllösungen with passivating N or in cold formed parts with lubricants and optionally lubricant carrier salts, such as borax or lime-treated.
Das erfindungsgemäße Verfahren hat sich insbesondere als Vorbereitung für die spanlose Kaltumformung bewährt. Es ist jedoch auch mit Vorteil auf den übrigen Anwendungsgebieten der Phosphatierung, z.B. Korrosionsschutz, Erleichterung der gleitenden Reibung, einzusetzen.The method according to the invention has proven particularly useful as a preparation for non-cutting cold forming. However, it is also advantageous in the other fields of application of phosphating, e.g. Use corrosion protection, to facilitate sliding friction.
Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
Stahlbleche der Qualität U St 1305 m wurden wir folgt behandelt:
- - Entfetten mittels Perchloräthylendampf
- - Beizen in 20%iger H2SO4 bei 60°C 5 min
- - Spülen mit kaltem Wasser
- - Phosphatieren im Tauchen in Bad A bzw. B bzw. C bei 650C und einer Behandlungszeit von 10 min
- - Spülen mit kaltem Wasser
- - Trocknen mittels Preßluft
- - Degreasing using perchlorethylene vapor
- - Pickling in 20% H 2 SO 4 at 60 ° C for 5 min
- - Rinse with cold water
- - Phosphating while diving in bath A or B or C at 65 0 C and a treatment time of 10 min
- - Rinse with cold water
- - Drying using compressed air
Die Phosphatierungsbäder hatten folgende Zusammensetzung:
Bad A war sulfatfrei und diente als Vergleich.Bad A was sulfate-free and served as a comparison.
In den Bädern B bzw. C waren die Sulfationen über ZnSO4 · 7H20 bzw. Na2S04 eingebracht worden.In baths B and C, the sulfate ions had been introduced over ZnSO 4 · 7H 2 0 and Na 2 S0 4, respectively.
Wie ein Vergleich der Schichtgewichte zeigt, sind die unter Verwendung von Sulfationen enthaltenden Bädern erzeugten Phosphatschichten von erheblich höherer Dicke.As a comparison of the layer weights shows, the phosphate layers produced using baths containing sulfate ions are of considerably greater thickness.
Bei der Phosphatierung von Kaltstauchdraht für die Kaltmassivumformung auf Mehrstufenpressen für die Schraubenfertigung wurde festgestellt, daß mit dem Bad A behandelter Draht an den stark beanspruchten Stellen metallisch blanke Stellen auftraten, daß also die Phosphatschicht komplett entfernt worden war. Demgegenüber lieferten die mit den Bädern B und C behandelten Kaltstauchdrähte auch nach kompletter Verformung Schrauben, die noch an allen Stellen mit schließenden, einwandfreien, fest verankerten Phosphatschichten versehen waren.When phosphating cold heading wire for cold massive forming on multi-stage presses for screw production, it was found that wire treated with Bad A had bare metal spots at the highly stressed points, so that the phosphate layer had been completely removed. In contrast, the cold heading wires treated with baths B and C supplied screws even after complete deformation, which were still provided with closing, perfect, firmly anchored phosphate layers at all points.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3108484 | 1981-03-06 | ||
| DE19813108484 DE3108484A1 (en) | 1981-03-06 | 1981-03-06 | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0059994A1 true EP0059994A1 (en) | 1982-09-15 |
| EP0059994B1 EP0059994B1 (en) | 1984-12-27 |
Family
ID=6126487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82200190A Expired EP0059994B1 (en) | 1981-03-06 | 1982-02-18 | Process for the production of phosphate coatings on metal surfaces |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4416705A (en) |
| EP (1) | EP0059994B1 (en) |
| JP (1) | JPS6045705B2 (en) |
| CA (1) | CA1175606A (en) |
| DE (2) | DE3108484A1 (en) |
| GB (1) | GB2094356B (en) |
| IT (1) | IT1150234B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3245411A1 (en) * | 1982-12-08 | 1984-07-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METAL GOODS |
| JPS619580A (en) * | 1984-06-25 | 1986-01-17 | Nippon Parkerizing Co Ltd | Treating solution for blackened phosphate film |
| CA1257527A (en) * | 1984-12-20 | 1989-07-18 | Thomas W. Tull | Cold deformation process employing improved lubrication coating |
| JPS63270478A (en) * | 1986-12-09 | 1988-11-08 | Nippon Denso Co Ltd | Phosphating method |
| ES2058464T3 (en) * | 1988-02-03 | 1994-11-01 | Metallgesellschaft Ag | PROCEDURE FOR THE GENERATION OF PHOSPHATE COATING ON METALS. |
| IT1295500B1 (en) * | 1997-10-21 | 1999-05-12 | Pierangelo Girardello | PROCEDURE FOR PROCESSING METALS AND PRODUCT OBTAINED WITH THIS PROCEDURE. |
| KR20190043155A (en) | 2016-08-24 | 2019-04-25 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Alkaline compositions for treating metal substrates |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2106626A1 (en) * | 1970-03-04 | 1971-09-23 | Metallgesellschaft Ag | Process for the production of a phosphate coating on metal surfaces |
| US4071379A (en) * | 1976-01-28 | 1978-01-31 | Imperial Chemical Industries Limited | Phosphating method |
| DE2239813B2 (en) * | 1971-09-20 | 1980-03-20 | Metallgesellschaft Ag, 6000 Frankfurt | Process for supplementing a solution containing zinc phosphate and chlorate for spray phosphating |
| EP0019430A1 (en) * | 1979-05-11 | 1980-11-26 | Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America | Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1159728B (en) * | 1954-04-24 | 1963-12-19 | Metallgesellschaft Ag | Process for applying phosphate coatings |
| DE1231523B (en) * | 1962-03-20 | 1966-12-29 | Metallgesellschaft Ag | Process for improving a phosphate coating applied to sheet metal and strips made of iron and steel for electrical insulation |
| DE1521879B2 (en) * | 1966-07-12 | 1975-08-28 | Metallgesellschaft Ag, 6000 Frankfurt | Process for applying phosphate coatings to iron and steel |
| DE1796102A1 (en) * | 1968-08-31 | 1972-02-17 | Metallgesellschaft Ag | Process for applying a phosphate coating to surfaces of iron and steel |
| GB1296883A (en) * | 1970-03-04 | 1972-11-22 |
-
1981
- 1981-03-06 DE DE19813108484 patent/DE3108484A1/en not_active Withdrawn
-
1982
- 1982-02-15 JP JP57022578A patent/JPS6045705B2/en not_active Expired
- 1982-02-18 DE DE8282200190T patent/DE3261654D1/en not_active Expired
- 1982-02-18 EP EP82200190A patent/EP0059994B1/en not_active Expired
- 1982-02-26 CA CA000397227A patent/CA1175606A/en not_active Expired
- 1982-02-26 US US06/352,925 patent/US4416705A/en not_active Expired - Fee Related
- 1982-03-03 IT IT19938/82A patent/IT1150234B/en active
- 1982-03-05 GB GB8206579A patent/GB2094356B/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2106626A1 (en) * | 1970-03-04 | 1971-09-23 | Metallgesellschaft Ag | Process for the production of a phosphate coating on metal surfaces |
| DE2239813B2 (en) * | 1971-09-20 | 1980-03-20 | Metallgesellschaft Ag, 6000 Frankfurt | Process for supplementing a solution containing zinc phosphate and chlorate for spray phosphating |
| US4071379A (en) * | 1976-01-28 | 1978-01-31 | Imperial Chemical Industries Limited | Phosphating method |
| EP0019430A1 (en) * | 1979-05-11 | 1980-11-26 | Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America | Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2094356A (en) | 1982-09-15 |
| IT8219938A0 (en) | 1982-03-03 |
| US4416705A (en) | 1983-11-22 |
| DE3261654D1 (en) | 1985-02-07 |
| JPS57152473A (en) | 1982-09-20 |
| DE3108484A1 (en) | 1982-09-23 |
| GB2094356B (en) | 1984-08-08 |
| JPS6045705B2 (en) | 1985-10-11 |
| IT1150234B (en) | 1986-12-10 |
| CA1175606A (en) | 1984-10-09 |
| EP0059994B1 (en) | 1984-12-27 |
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