EP0258922A1 - Process for producing phosphate coatings and their use - Google Patents
Process for producing phosphate coatings and their use Download PDFInfo
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- EP0258922A1 EP0258922A1 EP87201522A EP87201522A EP0258922A1 EP 0258922 A1 EP0258922 A1 EP 0258922A1 EP 87201522 A EP87201522 A EP 87201522A EP 87201522 A EP87201522 A EP 87201522A EP 0258922 A1 EP0258922 A1 EP 0258922A1
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- Prior art keywords
- zinc
- phosphating
- chlorate
- accelerator
- phosphate
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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
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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
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
Definitions
- the invention relates to a process for the production of phosphate layers on surfaces which consist partially or entirely of zinc or zinc alloys by means of zinc, phosphate, accelerator and nickel-containing phosphating solutions in dipping or flooding, and its application to the preparation of the surfaces for painting, in particular the Electro dip painting.
- Phosphating solutions for the phosphating of surfaces consisting at least partially of zinc or zinc alloys contain, in particular, zinc and phosphate as components determining the layer formation.
- other cations such as nickel, copper, calcium, manganese and alkali metal can be present to modify the layer formation.
- oxidizing agents e.g. from the group nitrate, chlorate, nitrite, peroxide, organic nitro compounds.
- Other possible additives include Fluoride, complex fluoride, chloride, organic polyhydroxycarboxylic acid, complex phosphates and surfactants.
- the baths are used in the immersion, spraying / immersion and spraying process at temperatures of typically 30 to 70 ° C. and treatment times of, for example, 0.5 to 5 minutes (EP - A - 69 950).
- EP-A-137 540 provides for the electrolytic production of zinc coatings on steel with a sulfuric acid electrolyte solution which contains one or more oxygen acids of the sulfur with an oxidation number of the sulfur of +5 to + 1 contains to work.
- Suitable acids of this type are e.g. sulfuric acid, sulfoxylic acid, dithionic acid and thiosulfuric acid.
- the object of the invention is therefore to design the phosphating process itself in such a way that the formation of specks on any zinc or zinc alloy surfaces is avoided.
- 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 surface is brought into contact with a phosphating solution which, when using chlorate as an accelerator, is practically free of nitrate and nitrite and when using nitrate and / or nitrite as an accelerator is kept practically free of chlorate and chloride.
- the method according to EP-A-69 950 provides, inter alia, for the phosphating of galvanized steel with phosphating solutions which must contain chlorate but expediently also contain nitrate (cf. Examples 1 and 3).
- a further content of nitrate is prescribed in addition to a content of chlorate.
- galvanized steel only provides for a content of nitrite or nitrobenzenesulfonate, but it is pointed out that the use of further oxidation accelerators, for example chlorate, is possible and can be advantageous.
- EP - A - l2l 274 also designated as suitable for the treatment of zinc and zinc alloys works with nitrite accelerated phosphating solutions.
- chlorate is also said to be necessary or desirable.
- any phosphating solutions based on zinc phosphate can be used to carry out the phosphating. They can belong to the so-called low zinc as well as the normal zinc technology. That is, the surfaces can with a phosphating solution in which the weight ratio of Zn to P2O5 is set to l: (8 to 85), or with a phosphating solution in which the weight ratio of Zn to P2O5 is set to l: (0.3 to ⁇ 8).
- phosphating processes result, which are characterized by a higher phosphating speed in comparison to the low zinc processes.
- the phosphate layers they produce have good properties for a wide range of applications in the areas of corrosion protection and non-cutting cold forming.
- aqueous acidic solutions based on zinc phosphate to be used in the context of the invention contain primary zinc phosphate, optionally alkali metal phosphate, and a certain amount of free acid which is matched to the respective bath concentration, type of application and bath temperature.
- the pH of the baths is between 2.0 and 3.9, depending on the process conditions.
- the phosphating solutions can also contain other cations known in phosphating technology, for example Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH4 and others.
- concentrations of the most important of these ions should be: at Mn and Ca up to 5 g / l, preferably up to 2.1 g / l, at Fe (II) up to 8 g / l, preferably up to 5 g / l.
- the use of other anions different from phosphate for example SO4, F, BF4, SiF6, citrate, tartrate, etc., may be necessary or desirable.
- the contact time for the phosphating solution used in the immersion treatment is usually between 1 and 10 minutes. When treating zinc or zinc alloys alone, shorter treatment times, e.g. from 2 to 30 sec., sufficient.
- the temperature of the phosphating solution is approximately 30 to 60 ° C. The lower the temperature, the longer the contact time.
- the measures customary in connection with phosphating processes can also be used in the present process. These are in particular degreasing and rust removal, pre-rinsing to activate the formation of the phosphate layer and after-treatment with rinsing solutions based on Cr (VI) and / or Cr (III) etc. or with impregnating agents such as rust protection oils, waxes and synthetic resins.
- the stock solution mentioned under 5. was modified by adding NO3, ClO3, Cl, nickel and nitrobenzenesulfonate (NBS) according to the table below.
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von Phosphatschichten auf Oberflächen, die teilweise oder ganz aus Zink oder Zinklegierungen bestehen, mittels Zink, Phosphat, Beschleuniger sowie Nickel enthaltenden Phosphatierungslösungen im Tauchen oder Fluten sowie dessen Anwendung auf die Vorbereitung der Oberflächen für die Lackierung, insbesondere die Elektrotauchlackierung.The invention relates to a process for the production of phosphate layers on surfaces which consist partially or entirely of zinc or zinc alloys by means of zinc, phosphate, accelerator and nickel-containing phosphating solutions in dipping or flooding, and its application to the preparation of the surfaces for painting, in particular the Electro dip painting.
Phosphatierungslösungen für die Phosphatierung von mindestens teilweise aus Zink oder Zinklegierungen bestehenden Oberflächen enthalten insbesondere Zink und Phosphat als die Schichtausbildung bestimmende Komponenten. Daneben können zur Modifizierung der Schichtbildung noch weitere Kationen, wie Nickel, Kupfer, Kalzium, Mangan und Alkalimetall zugegen sein. Zur Beschleunigung der Schichtbildung werden Oxidationsmittel, z.B. aus der Gruppe Nitrat, Chlorat, Nitrit, Peroxid, organische Nitroverbindungen, mitverwendet. Weitere mögliche Zusätze sind u.a. Fluorid, komplexes Fluorid, Chlorid, organische Polyhydroxykarbonsäure, komplexe Phosphate und Tenside. Die Bäder werden im Tauch- Spritz-/Tauch- und Spritzverfahren bei Temperaturen von üblicherweise 30 bis 70°C und Behandlungszeiten von beispielsweise 0,5 bis 5 min angewendet (EP - A - 69 950).Phosphating solutions for the phosphating of surfaces consisting at least partially of zinc or zinc alloys contain, in particular, zinc and phosphate as components determining the layer formation. In addition, other cations such as nickel, copper, calcium, manganese and alkali metal can be present to modify the layer formation. To accelerate layer formation, oxidizing agents, e.g. from the group nitrate, chlorate, nitrite, peroxide, organic nitro compounds. Other possible additives include Fluoride, complex fluoride, chloride, organic polyhydroxycarboxylic acid, complex phosphates and surfactants. The baths are used in the immersion, spraying / immersion and spraying process at temperatures of typically 30 to 70 ° C. and treatment times of, for example, 0.5 to 5 minutes (EP - A - 69 950).
Nach der Phosphatierung derartiger Oberflächen werden häufig auf der an sich einheitlich deckenden Phosphatschicht kleine weißliche Stippen beobachtet, die sich bei miskroskopischer Betrachtung als Beizgrübchen mit am Rand angehäuften Kristallen erweisen. Während des Kontaktes mit der Phosphatierungslösung überzieht sich die Zinkoberfläche mit zunehmender Phosphatierzeit praktisch vollständig mit einer Phosphatschicht, wobei allerdings aus noch unbekannten Gründen einzelne Punkte mit einem Durchmesser von 0,l bis l mm verbleiben, an denen die Beizwirkung der Phosphatierungslösung andauert. Das hohe, aus den Beizgrübchen stammende Zinkionenangebot führt am Rande der Grübchen zur Ausfällung von tertiärem Zinkphosphat, das wie der Rand eines Kraters aufwächst. Bei der anschließenden Lackierung markieren sich die Stippen als kleine Erhebungen im Lackfilm und verursachen kostspielige Schleifarbeit. Die vorgenannte Erscheinung tritt nicht nur bei durchgehend aus Zink oder Zinklegierungen bestehenden Oberflächen auf, sondern auch bei Verbundmetallen, deren Oberfläche nur teilweise aus Zink oder Zinklegierung besteht.After the phosphating of such surfaces, small whitish specks are frequently observed on the phosphate layer, which is uniformly covering itself crystals heaped on the edge. During contact with the phosphating solution, the zinc surface practically completely covers with a phosphate layer with increasing phosphating time, although for unknown reasons individual points with a diameter of 0.1 to 1 mm remain at which the pickling action of the phosphating solution persists. The high supply of zinc ions from the pickling dimples leads to the precipitation of tertiary zinc phosphate on the edge of the dimples, which grows up like the edge of a crater. During the subsequent painting, the specks mark as small elevations in the paint film and cause expensive sanding work. The aforementioned phenomenon occurs not only in the case of surfaces consisting entirely of zinc or zinc alloys, but also in the case of composite metals, the surface of which consists only partially of zinc or zinc alloy.
Um eine derartige Stippenbildung zu vermeiden, sieht das Verfahren gemäß EP - A - l37 540 vor, bei der elektrolytischen Erzeugung von Zinküberzügen auf Stahl mit einer schwefelsauren Elektrolytlösung, die eine oder mehrere Sauerstoffsäuren des Schwefels mit einer Oxidationszahl des Schwefels von +5 bis +l enthält, zu arbeiten. Geeignete Säuren dieser Art sind z.B. schwefelige Säure, Sulfoxylsäure, dithionige Säure und Thioschwefelsäure.In order to avoid such speck formation, the process according to EP-A-137 540 provides for the electrolytic production of zinc coatings on steel with a sulfuric acid electrolyte solution which contains one or more oxygen acids of the sulfur with an oxidation number of the sulfur of +5 to + 1 contains to work. Suitable acids of this type are e.g. sulfuric acid, sulfoxylic acid, dithionic acid and thiosulfuric acid.
Obgleich dieses Verfahren erhebliche Vorteile bei der Vermeidung von Stippen besitzt, ist es naturgemäß nicht einsetzbar, wenn die Oberflächen bereits verzinkt sind bzw. wenn das Werkstück aus massivem Zink bzw. aus einer massiven Zinklegierungen besteht.Although this method has considerable advantages in avoiding specks, it cannot of course be used if the surfaces are already galvanized or if the workpiece is made of solid zinc or of a solid zinc alloy.
Aufgabe der Erfindung ist es daher, das Phosphatierverfahren selbst derart auszugestalten, daß die Ausbildung von Stippen auf beliebigen Zink- oder Zinklegierungsoberflächen unterbleibt.The object of the invention is therefore to design the phosphating process itself in such a way that the formation of specks on any zinc or zinc alloy surfaces is avoided.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die bei Einsatz von Chlorat als Beschleuniger praktisch frei von Nitrat und Nitrit und bei Einsatz von Nitrat und/oder Nitrit als Beschleuniger praktisch frei von Chlorat und Chlorid gehalten wird.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 surface is brought into contact with a phosphating solution which, when using chlorate as an accelerator, is practically free of nitrate and nitrite and when using nitrate and / or nitrite as an accelerator is kept practically free of chlorate and chloride.
Zwar ist es aus der Literatur bekannt, daß außer Oberflächen aus Eisen und Stahl auch solche aus Zink oder Zinklegierungen mit Phosphatierungslösungen behandelt werden können, die Nickel sowie lediglich Chlorat oder lediglich Nitrat bzw. Nitrit enthalten können. Jedoch ist hierbei nicht der ursächliche Zusammenhang zwischen Entstehung von Stippen und deren Vermeidung gemäß der vorstehend genannten Lehre erkannt worden.It is known from the literature that, in addition to surfaces made of iron and steel, those made of zinc or zinc alloys can also be treated with phosphating solutions which may contain nickel and only chlorate or only nitrate or nitrite. However, the causal relationship between the formation of specks and their avoidance has not been recognized in accordance with the above teaching.
Beispielsweise sieht das Verfahren gemäß EP - A - 69 950 u.a. die Phosphatierung von verzinktem Stahl mit Phosphatierungslösungen vor, die Chlorat enthalten müssen, aber zweckmäßigerweise auch Nitrat enthalten (vgl. Beispiele l und 3). Im Verfahren entsprechend EP - A - 39 093, das auch der Mitbehandlung von Zinkoberflächen dient, ist außer einem Gehalt an Chlorat auch ein weiterer Gehalt von Nitrat vorgeschrieben. Das in der EP - A - l54 367 beschriebene Verfahren zur Phosphatierung von u.a. verzinktem Stahl sieht gemäß Anspruch l nur einen Gehalt von Nitrit oder Nitrobenzolsulfonat zwingend vor, jedoch ist darauf hingewiesen, daß die Mitverwendung weiterer Oxidationsbeschleuniger, z.B. Chlorat, möglich ist und vorteilhaft sein kann.For example, the method according to EP-A-69 950 provides, inter alia, for the phosphating of galvanized steel with phosphating solutions which must contain chlorate but expediently also contain nitrate (cf. Examples 1 and 3). In the process according to EP-A-39 093, which also serves to treat zinc surfaces, a further content of nitrate is prescribed in addition to a content of chlorate. The process for the phosphating of, inter alia, described in EP - A - 1554 367 According to claim 1, galvanized steel only provides for a content of nitrite or nitrobenzenesulfonate, but it is pointed out that the use of further oxidation accelerators, for example chlorate, is possible and can be advantageous.
Das u.a. auch für die Behandlung von Zink und Zinklegierungen als geeignet bezeichnete Verfahren der EP - A - l2l 274 arbeitet mit nitritbeschleunigten Phosphatierlösungen. Die Mitverwendung u.a. auch von Chlorat wird als erforderlich bzw. wünschenswert bezeichnet. Im wesentlichen das gleiche gilt für das Verfahren zur Vorbehandlung von Metalloberflächen für die Elektrotauchlackierung gemäß EP - A - l09 ll0.The u.a. The method of EP - A - l2l 274 also designated as suitable for the treatment of zinc and zinc alloys works with nitrite accelerated phosphating solutions. The use among other things chlorate is also said to be necessary or desirable. Essentially the same applies to the process for the pretreatment of metal surfaces for electrocoating according to EP-A-l09 ll0.
Außer den vorstehend dargelegten Bemerkungen hinsichtlich der Beschleuniger ist ergänzend zu beachten, daß weitere für die vorliegende Erfindung wesentliche Kriterien, nämlich daß die Lehre für Nickelionen enthaltende und im Tauch- bzw. Flutverfahren eingesetzte Phosphatierungslösungen gilt, bei der vorstehenden Behandlung des Standes der Technik unberücksichtigt geblieben sind.In addition to the comments regarding the accelerators set out above, it should also be noted that further criteria essential to the present invention, namely that the teaching applies to phosphating solutions containing nickel ions and used in the immersion or flooding process, have not been taken into account in the above treatment of the prior art are.
Zur Durchführung der Phosphatierung sind beliebige Phosphatierungslösungen auf Basis Zinkphosphat einsetzbar. Sie können sowohl der sogenannten Niedrigzink- als auch der Normalzink-Technologie angehören. Das heißt, die Oberflächen können mit einer Phosphatierungslösung, in der das Gewichtsverhältnis von Zn zu P₂O₅ auf l : (8 bis 85) eingestellt ist, oder aber mit einer Phosphatierungslösung, in der das Gewichtsverhältnis von Zn zu P₂O₅ auf l : (0,3 bis < 8) eingestellt ist, in Berührung gebracht werden.Any phosphating solutions based on zinc phosphate can be used to carry out the phosphating. They can belong to the so-called low zinc as well as the normal zinc technology. That is, the surfaces can with a phosphating solution in which the weight ratio of Zn to P₂O₅ is set to l: (8 to 85), or with a phosphating solution in which the weight ratio of Zn to P₂O₅ is set to l: (0.3 to <8).
Im ersten Fall entstehen, wenn die Oberflächen teilweise aus Stahl bestehen, auf Stahl Phosphatschichten mit einem hohen Anteil an Phosphophyllit zu Hopeit. Diese Überzüge eignen sich wegen ihres ausgezeichneten Korrosionsschutzes insbesondere als Vorbereitung für die Lackierung, wobei die besten Schutzeigenschaften in Verbindung mit der kathodischen Elektrotauchlackierung erzielt werden.In the first case, if the surfaces are partly made of steel, phosphate layers with a high proportion of phosphophyllite to hopite are formed on steel. Because of their excellent corrosion protection, these coatings are particularly suitable as a preparation for painting, whereby the best protective properties are achieved in connection with the cathodic electrocoating.
Im zweiten Fall resultieren Phosphatierverfahren, die sich im Vergleich zu den Niedrigzink-Verfahren durch eine höhere Phosphatiergeschwindigkeit auszeichnen. Die mit ihnen erzeugten Phosphatschichten besitzen gute Eigenschaften für ein breites Anwendungsspektrum aus den Bereichen des Korrosionsschutzes und der spanlosen Kaltumformung.In the second case, phosphating processes result, which are characterized by a higher phosphating speed in comparison to the low zinc processes. The phosphate layers they produce have good properties for a wide range of applications in the areas of corrosion protection and non-cutting cold forming.
Die im Rahmen der Erfindung zu verwendenden wäßrigen sauren Lösungen auf Basis Zinkphosphat enthalten primäres Zinkphosphat, ggf. Alkaliphosphat, und eine gewisse, auf die jeweilige Badkonzentration, Anwendungsart und Badtemperatur abgestimmte Menge an freier Säure. Der pH-Wert der Bäder liegt, abhängig von den Verfahrensbedingungen, etwa zwischen 2,0 und 3,9.The aqueous acidic solutions based on zinc phosphate to be used in the context of the invention contain primary zinc phosphate, optionally alkali metal phosphate, and a certain amount of free acid which is matched to the respective bath concentration, type of application and bath temperature. The pH of the baths is between 2.0 and 3.9, depending on the process conditions.
Die Phosphatierungslösungen können ferner in der Phosphatiertechnik bekannte weitere Kationen, z.B. Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH₄ u.a., enthalten. Die Konzentrationen der wichtigsten dieser Ionen sollten sein: bei Mn und Ca bis 5 g/l, vorzugsweise bis 2,g/l, bei Fe(II) bis 8 g/l, vorzugsweise bis 5 g/l. Zur Einstellung des Säureverhältnisses und zur Erzielung spezieller technischer Effekte kann die Mitverwendung weiterer, von Phosphat verschiedener Anionen, z.B. SO₄, F, BF₄, SiF₆, Citrat, Tartrat u.a., erforderlich bzw. wünschenswert sein.The phosphating solutions can also contain other cations known in phosphating technology, for example Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH₄ and others. The concentrations of the most important of these ions should be: at Mn and Ca up to 5 g / l, preferably up to 2.1 g / l, at Fe (II) up to 8 g / l, preferably up to 5 g / l. To adjust the acid ratio and to achieve special technical effects, the use of other anions different from phosphate, for example SO₄, F, BF₄, SiF₆, citrate, tartrate, etc., may be necessary or desirable.
Die Kontaktzeit für die in der Tauchbehandlung zum Einsatz kommenden Phosphatierungslösung liegt üblicherweise zwischen l und l0 min. Bei alleiniger Behandlung von Zink oder Zinklegierungen sind auch geringere Behandlungszeiten, z.B. von 2 bis 30 sec., ausreichend. Die Temperatur der Phosphatierungslösung beträgt etwa 30 bis 60°C. Je niedriger die Temperatur ist, um so länger ist üblicherweise die Kontaktzeit.The contact time for the phosphating solution used in the immersion treatment is usually between 1 and 10 minutes. When treating zinc or zinc alloys alone, shorter treatment times, e.g. from 2 to 30 sec., sufficient. The temperature of the phosphating solution is approximately 30 to 60 ° C. The lower the temperature, the longer the contact time.
Im übrigen sind auch beim vorliegenden Verfahren die im Zusammenhang mit Phosphatierverfahren üblichen Maßnahmen anwendbar. Hierbei handelt es sich insbesondere um Entfettung und Entrostung, Vorspülung zwecks Aktivierung der Phosphatschichtausbildung und Nachbehandlung mit Nachspüllösungen auf Basis Cr(VI) und/oder Cr(III) etc. bzw. mit Imprägniermitteln, wie Rostschutzölen, -Wachsen und Kunstharzen.Otherwise, the measures customary in connection with phosphating processes can also be used in the present process. These are in particular degreasing and rust removal, pre-rinsing to activate the formation of the phosphate layer and after-treatment with rinsing solutions based on Cr (VI) and / or Cr (III) etc. or with impregnating agents such as rust protection oils, waxes and synthetic resins.
Die Erfindung wird anhand der Beispiele beispielsweise und näher erläutert.The invention is illustrated by way of example and in more detail.
Beidseitig elektrolytisch verzinkte Stahlbleche (A) sowie Verbundmetalle aus Stahlblech und verzinktem Stahlblech (B) wurden nach folgendem Arbeitsgang behandelt:
- l.) Perdampfentfettung
- 2.) Reinigung mit einem alkalischen Reiniger bei 80°C während 9,5 min. Tauchen
- 3.) Spülung mit Kaltwasser im Tauchen
- 4.) Aktivierung mit einer Titanphosphatlösung während l min. im Tauchen
- 5.) Tauchphosphatierung bei 60°C mit einer Stammlösung, die
l,2 g/l Zn
l5 g/l P₂O₅
0,03 g/l Fe(III)
3-6 g/l Na
enthält und
freie Säure 2,l Punkte,
Gesamtsäure 26 Punkte
sowie einen S-Wert von 0,l aufweist - 6.) Spülung mit Kaltwasser im Tauchen
- 7.) Trocknung im Ofen während l5 min
- l.) Steam degreasing
- 2.) Cleaning with an alkaline cleaner at 80 ° C for 9.5 min. Diving
- 3.) Rinsing with cold water while diving
- 4.) Activation with a titanium phosphate solution for 1 min. in diving
- 5.) Dip phosphating at 60 ° C with a stock solution
1.2 g / l Zn
l5 g / l P₂O₅
0.03 g / l Fe (III)
3-6 g / l Na
contains and
free acid 2, l points,
Total acidity 26 points
and has an S value of 0.1 - 6.) Rinsing with cold water while diving
- 7.) Drying in the oven for l5 min
Die unter 5.) genannte Stammlösung wurde durch Zugabe von NO₃, ClO₃, Cl, Nickel und Nitrobenzolsulfonat (NBS) entsprechend der nachfolgenden Tabelle modifiziert.
Die vorstehenden Versuche zeigen, daß die Bildung von Stippen vermieden wird, wenn beim Einsatz von Chlorat enthaltenden Phosphatierungslösungen auf weitgehende Freiheit von NO₃ (Beispiele ll bis l3) und beim Einsatz von Nitrat enthaltenden Phosphatierungslösungen auf weitgehende Freiheit von Chlorat bzw. Chlorid (Beispiele 9 und l0) geachtet wird.The above experiments show that the formation of Spotting is avoided if the use of chlorate-containing phosphating solutions is largely free of NO₃ (Examples ll to l3) and the use of nitrate-containing phosphating solutions is largely free of chlorate or chloride (Examples 9 and l0).
Bei Verwendung von sowohl Chlorat als auch Nitrat (Beispiel l4) bzw. von Nitrat als auch Chlorid (Beispiel l0) enthaltenden Phosphatierungslösungen tritt hingegen eine beträchtliche Stippenbildung auf. Die Beispiele l3 und l4 lassen insbesondere erkennen, daß die Stippenbildung nicht durch den Gehalt an Nitrobenzolsulfonat verursacht wird.When using both chlorate and nitrate (example l4) or nitrate and chloride (example l0) containing phosphating solutions, on the other hand, considerable speck formation occurs. Examples 13 and 14 show in particular that the formation of specks is not caused by the content of nitrobenzenesulfonate.
Aus den Beispielen l bis 6 ist schließlich ersichtlich, daß das Problem der Stippenbildung bei Einsatz von Phosphatierungslösungen, die nickelfrei sind, nicht auftritt.Finally, it can be seen from Examples 1 to 6 that the problem of speck formation does not arise when using phosphating solutions which are nickel-free.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3630246 | 1986-09-05 | ||
| DE19863630246 DE3630246A1 (en) | 1986-09-05 | 1986-09-05 | METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0258922A1 true EP0258922A1 (en) | 1988-03-09 |
Family
ID=6308977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87201522A Withdrawn EP0258922A1 (en) | 1986-09-05 | 1987-08-11 | Process for producing phosphate coatings and their use |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0258922A1 (en) |
| JP (1) | JPS63145784A (en) |
| DE (1) | DE3630246A1 (en) |
| GB (1) | GB2196024A (en) |
| ZA (1) | ZA876589B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0304108A1 (en) * | 1987-08-19 | 1989-02-22 | Metallgesellschaft Ag | Metal-phosphating process |
| WO1990012901A1 (en) * | 1989-04-21 | 1990-11-01 | Henkel Kommanditgesellschaft Auf Aktien | Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films |
| WO1997016581A2 (en) * | 1995-10-27 | 1997-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Low-nitrate, manganese-free zinc phosphatization |
| WO1997030189A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Zinc-phosphatizing method using low nickel and/or cobalt concentrations |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0730455B2 (en) * | 1988-09-27 | 1995-04-05 | 日本パーカライジング株式会社 | Phosphate chemical treatment liquid |
| DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
| DE4241134A1 (en) * | 1992-12-07 | 1994-06-09 | Henkel Kgaa | Process for phosphating metal surfaces |
| WO2000008224A2 (en) * | 1998-07-21 | 2000-02-17 | Brent International Plc | Nickel-zinc phosphate conversion coatings and process for making the same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2033717A5 (en) * | 1969-03-07 | 1970-12-04 | Parker Ste Continentale | |
| EP0056881A1 (en) * | 1981-01-22 | 1982-08-04 | Metallgesellschaft Ag | Method of phosphating metals |
| EP0111246A2 (en) * | 1982-12-08 | 1984-06-20 | Gerhard Collardin GmbH | Process for phosphatizing zinc-electroplated metal objects |
| EP0121274A1 (en) * | 1983-03-31 | 1984-10-10 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
| GB2148951A (en) * | 1983-11-02 | 1985-06-05 | Pyrene Chemical Services Ltd | Phosphating processes and compositions |
| US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
| EP0228151A1 (en) * | 1985-08-27 | 1987-07-08 | HENKEL CORPORATION (a Delaware Corp.) | Acidic, aqueous phosphate-coating solutions for use in a process for phosphate-coating metal surfaces |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1040806A (en) * | 1964-04-30 | 1966-09-01 | Pyrene Co Ltd | Improvements in painting metal surfaces |
| US3620949A (en) * | 1969-04-11 | 1971-11-16 | Balm Paints Ltd | Metal pretreatment and coating process |
| GB1542222A (en) * | 1977-01-06 | 1979-03-14 | Pyrene Chemical Services Ltd | Phosphate coating compositions |
| JPS5811514B2 (en) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | How to protect metal surfaces |
| JPS5811515B2 (en) * | 1979-05-11 | 1983-03-03 | 日本ペイント株式会社 | Composition for forming a zinc phosphate film on metal surfaces |
| GB2072225B (en) * | 1980-03-21 | 1983-11-02 | Pyrene Chemical Services Ltd | Process and composition for coating metal surfaces |
| DE3118375A1 (en) * | 1981-05-09 | 1982-11-25 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS AND ITS APPLICATION FOR PRE-TREATMENT FOR ELECTRO DIP PAINTING |
| US4498935A (en) * | 1981-07-13 | 1985-02-12 | Parker Chemical Company | Zinc phosphate conversion coating composition |
| DE3408577A1 (en) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
-
1986
- 1986-09-05 DE DE19863630246 patent/DE3630246A1/en not_active Withdrawn
-
1987
- 1987-08-11 EP EP87201522A patent/EP0258922A1/en not_active Withdrawn
- 1987-09-02 JP JP62218066A patent/JPS63145784A/en active Pending
- 1987-09-03 ZA ZA876589A patent/ZA876589B/en unknown
- 1987-09-04 GB GB08720788A patent/GB2196024A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2033717A5 (en) * | 1969-03-07 | 1970-12-04 | Parker Ste Continentale | |
| EP0056881A1 (en) * | 1981-01-22 | 1982-08-04 | Metallgesellschaft Ag | Method of phosphating metals |
| EP0111246A2 (en) * | 1982-12-08 | 1984-06-20 | Gerhard Collardin GmbH | Process for phosphatizing zinc-electroplated metal objects |
| EP0121274A1 (en) * | 1983-03-31 | 1984-10-10 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
| GB2148951A (en) * | 1983-11-02 | 1985-06-05 | Pyrene Chemical Services Ltd | Phosphating processes and compositions |
| US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
| EP0228151A1 (en) * | 1985-08-27 | 1987-07-08 | HENKEL CORPORATION (a Delaware Corp.) | Acidic, aqueous phosphate-coating solutions for use in a process for phosphate-coating metal surfaces |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0304108A1 (en) * | 1987-08-19 | 1989-02-22 | Metallgesellschaft Ag | Metal-phosphating process |
| WO1990012901A1 (en) * | 1989-04-21 | 1990-11-01 | Henkel Kommanditgesellschaft Auf Aktien | Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films |
| WO1997016581A2 (en) * | 1995-10-27 | 1997-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Low-nitrate, manganese-free zinc phosphatization |
| WO1997016581A3 (en) * | 1995-10-27 | 1997-06-19 | Henkel Kgaa | Low-nitrate, manganese-free zinc phosphatization |
| WO1997030189A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Zinc-phosphatizing method using low nickel and/or cobalt concentrations |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2196024A (en) | 1988-04-20 |
| JPS63145784A (en) | 1988-06-17 |
| DE3630246A1 (en) | 1988-03-10 |
| GB8720788D0 (en) | 1987-10-14 |
| ZA876589B (en) | 1989-05-30 |
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Inventor name: HAUFFE, DIETER |