EP0127204B1 - Phosphating process for composite metals - Google Patents
Phosphating process for composite metals Download PDFInfo
- Publication number
- EP0127204B1 EP0127204B1 EP84200398A EP84200398A EP0127204B1 EP 0127204 B1 EP0127204 B1 EP 0127204B1 EP 84200398 A EP84200398 A EP 84200398A EP 84200398 A EP84200398 A EP 84200398A EP 0127204 B1 EP0127204 B1 EP 0127204B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- phosphate
- zinc
- steel sheets
- composite metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 239000002184 metal Substances 0.000 title claims description 17
- 239000002131 composite material Substances 0.000 title claims description 14
- 150000002739 metals Chemical class 0.000 title claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 22
- 239000010959 steel Substances 0.000 claims description 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 17
- 239000010452 phosphate Substances 0.000 claims description 17
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 11
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 5
- 239000008397 galvanized steel Substances 0.000 claims description 5
- 238000005246 galvanizing Methods 0.000 claims description 4
- 238000005304 joining Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 21
- 239000011701 zinc Substances 0.000 description 16
- 238000007654 immersion Methods 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 12
- 230000009189 diving Effects 0.000 description 8
- 239000007921 spray Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 phosphate anions Chemical class 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—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 characterised by the process
Definitions
- the invention relates to a method for phosphating objects with cavities, which have been obtained by joining steel sheets and galvanized steel sheets or by partially galvanizing steel sheets (composite metals), using phosphating solutions based on zinc phosphate in diving.
- composite metals In industrial series production, surface-coated, in particular galvanized, steel sheets, so-called composite metals, are becoming increasingly important. Composite metals of this type are obtained by joining steel sheets and galvanized steel sheets and by partially galvanizing steel sheets. Similar to parts that only have steel or zinc surfaces, phosphating with solutions based on zinc phosphate is required before painting, especially electrocoating, to improve corrosion protection and paint adhesion.
- the formation of the phosphate layer is disturbed insofar as, depending on the phosphating process, an approximately 5 to 10 mm wide strip is formed on the steel side which bears a highly translucent, only imperfectly formed phosphate layer.
- Spraying and spraying / immersion processes cause less difficulties because of the imperfect formation of an electrochemical element.
- the abovementioned stripe generally does not occur, but the entire phosphate layer is often streaked and adversely affects the paint structure subsequently applied.
- phosphating solutions containing 0.5 to 1.5 g / l zinc, 5 to 30 g / l phosphate ions, 0.6 to 3 g / l manganese ions and conventional accelerators. to be treated first in diving and then in spraying (EP-OS 60 716).
- the immersion treatment should be at least 15 s, expediently 0.5 to 2 min, and the spray treatment at least 2 s, expediently 5 to 45 s.
- This method also does not satisfactorily phosphate composite metals.
- the object of the invention is to provide a method for phosphating objects with cavities, which have been obtained by joining steel sheets and galvanized steel sheets or by partial galvanizing of steel sheets (composite metals), which does not have the disadvantages of the aforementioned methods, but - without additional procedural effort - leads to a perfect closed phosphate layer.
- 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 objects for initiating the formation of the phosphate layer are pre-immersed in a phosphating solution based on zinc phosphate for a maximum of 30 s and then fed to the zone of the actual immersion phosphating.
- JP-A-81 119 780 It is known from JP-A-81 119 780 to pretreat cold-rolled or galvanized steel sheets with the same type of phosphating solution before the usual phosphating. However, this is not a process for phosphating composite metals, i.e. of objects that have both free steel and free zinc surfaces.
- any phosphating solutions based on zinc phosphate can be used to carry out the phosphating. You can belong to the so-called low zinc as well as the normal zinc technology. That is, the composite metals can with a phosphating solution in which the weight ratio of Zn to P 2 0 5 is set to 1: (8 to 85), or with a phosphating solution in which the weight ratio of Zn to P 2 0 5 to 1: (0.3 to 7) is set.
- 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.
- 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 and a certain amount of free acid which is matched to the respective bath concentration, type of application and bath temperature. Depending on the process conditions, the pH of the baths is approximately between 2.0. and 3.9.
- the baths can also known in the phosphating technology other cations, for. B. Ni, Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH4, etc. included.
- the use of other, different from phosphate anions, z. B. N0 3 , C10 3 , Cl, S0 4 , F, BF 4 , SiF 6 , citrate, tartrate, etc. may be necessary or desirable.
- the contact time for the phosphating solution used in the final immersion treatment is usually between 1 and 10 minutes.
- the temperature of the phosphating solution is approximately 30 to 60 ° C. The lower the temperature, the longer the contact time.
- An advantageous embodiment of the invention consists of spraying the objects (composite metals) with phosphating solution based on zinc phosphate during the feed to the immersion phosphating zone, and further adjusting the supply to the immersion phosphating zone and thus the spray treatment to a maximum of 30 s.
- This procedure has the advantage that fresh phosphating solution is available during the transfer of the metal surface into the final immersion treatment in order to form a constant liquid film on the metal surface. It is thus avoided that liquid films of different thicknesses are present on the metal surface as the liquid runs off.
- the advantage of the aforementioned measure is particularly evident in the formation of uniform phosphate layers.
- 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 phosphate layer formation is flawless both in the vicinity of the zinc surface and on the entire steel surface.
- the phosphate layer on the steel surface remains closed after prolonged diving, but it is incomplete and translucent in the area of action of the zinc surface.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
Die Erfindung betrifft ein Verfahren zum Phosphatieren von Gegenständen mit Hohlräumen, welche durch Zusammenfügen von Stahlblechen und verzinkten Stahlblechen oder durch teilweises Verzinken von Stahlblechen erhalten worden sind (Verbundmetalle), unter Verwendung von Phosphatierungslösungen auf Basis Zinkphosphat im Tauchen.The invention relates to a method for phosphating objects with cavities, which have been obtained by joining steel sheets and galvanized steel sheets or by partially galvanizing steel sheets (composite metals), using phosphating solutions based on zinc phosphate in diving.
In der industriellen Serienfertigung finden oberflächenveredelte, insbesondere verzinkte, Stahlbleche, sogenannte Verbundmetalle, zunehmend an Bedeutung. Derartige Verbundmetalle werden durch Zusammenfügen von Stahlblechen und verzinkten Stahlblechen sowie durch teilweises Verzinken von Stahlblechen erhalten. Ähnlich wie allein Stahl- oder Zinkoberflächen aufweisende Teile ist vor der Lackierung, insbesondere Elektrotauchlackierung, eine Phosphatierung mit Lösungen auf Basis Zinkphosphat zur Verbesserung des Korrosionsschutzes und der Lackhaftung erforderlich.In industrial series production, surface-coated, in particular galvanized, steel sheets, so-called composite metals, are becoming increasingly important. Composite metals of this type are obtained by joining steel sheets and galvanized steel sheets and by partially galvanizing steel sheets. Similar to parts that only have steel or zinc surfaces, phosphating with solutions based on zinc phosphate is required before painting, especially electrocoating, to improve corrosion protection and paint adhesion.
Die Besonderheit bei der Phosphatierung von Zink- und Stahloberflächen aufweisenden Verbundmetallen besteht darin, daß sich beim Kontakt mit der Phosphatierungslösung, insbesondere bei der Tauchbehandlung, ein elektrochemisches Element mit der Zinkoberfläche als Anode und der Stahloberfläche als Kathode ausbildet. Infolgedessen ist in unmittelbarer Nachbarschaft zur Zinkoberfläche die kathodische Stromdichte auf der Stahloberfläche so groß, daß der Phosphatiervorgang beeinträchtigt wird (W. Rausch, "Chemische Oberflächenbehandlung von verzinktem und zinkstaublackiertem Stahl für die kathodische Elektrotauchlackierung" Industrie Lackierbetrieb 49 (1981), Seite 413ff).The peculiarity of the phosphating of zinc and steel surfaces having composite metals is that an electrochemical element with the zinc surface as the anode and the steel surface as the cathode forms on contact with the phosphating solution, in particular during the immersion treatment. As a result, in the immediate vicinity of the zinc surface, the cathodic current density on the steel surface is so great that the phosphating process is impaired (W. Rausch, "Chemical surface treatment of galvanized and zinc dust-coated steel for cathodic electrocoating" Industrie Lackierbetrieb 49 (1981), page 413ff).
So wird bei der Tauchphosphatierung die Phosphatschichtausbildung insofern gestört, als je nach Phosphatierverfahren ein etwa 5 bis 10 mm breiter Streifen auf der Stahlseite entsteht, der eine stark durchscheinende, nur unvollkommen ausgebildete Phosphatschicht trägt.For example, in the case of immersion phosphating, the formation of the phosphate layer is disturbed insofar as, depending on the phosphating process, an approximately 5 to 10 mm wide strip is formed on the steel side which bears a highly translucent, only imperfectly formed phosphate layer.
Spritz- und Spritz/Tauchverfahren bereiten wegen der nur unvollkommenen Ausbildung eines elektrochemischen Elementes geringere Schwierigkeiten. Der vorgenannte Streifen entsteht im allgemeinen nicht, jedoch ist die gesamte Phosphatschicht häufig streifig und beeinträchtigt den nachfolgend aufgebrachten Lackaufbau nachteilig.Spraying and spraying / immersion processes cause less difficulties because of the imperfect formation of an electrochemical element. The abovementioned stripe generally does not occur, but the entire phosphate layer is often streaked and adversely affects the paint structure subsequently applied.
Speziell zur Behandlung von Verbundmetallen der vorgenannten Art ist es bekannt, mit Phosphatierungslösungen, die 0,5 bis 1,5 g/I Zink, 5 bis 30 g/I Phosphationen, 0,6 bis 3 g/I Manganionen und übliche Beschleuniger enthalten, zunächst im Tauchen und dann im Spritzen zu behandeln (EP-OS 60 716). Die Tauchbehandlung soll dabei mindestens 15 s, zweckmäßigerweise 0,5 bis 2 min, die Spritzbehandlung mindestens 2 s, zweckmäßigerweise 5 bis 45 s, betragen. Auch mit diesem Verfahren lassen sich Hohlräume aufweisende Verbundmetalle nicht in zufriedenstellenderweise Phosphatieren.Especially for the treatment of composite metals of the aforementioned type, it is known to use phosphating solutions containing 0.5 to 1.5 g / l zinc, 5 to 30 g / l phosphate ions, 0.6 to 3 g / l manganese ions and conventional accelerators. to be treated first in diving and then in spraying (EP-OS 60 716). The immersion treatment should be at least 15 s, expediently 0.5 to 2 min, and the spray treatment at least 2 s, expediently 5 to 45 s. This method also does not satisfactorily phosphate composite metals.
Aufgabe der Erfindung ist es, ein Verfahren zum Phosphatieren von Gegenständen mit Hohlräumen, welche durch Zusammenfügen von Stahlblechen und verzinkten Stahlblechen oder durch teilweises Verzinken von Stahlblechen erhalten worden sind (Verbundmetalle), bereitzustellen, das die Nachteile der vorgenannten Verfahren nicht besitzt, sondern - ohne zusätzlichen verfahrensmäßigen Aufwand - zu einer einwandfreien geschlossenen Phosphatschicht führt.The object of the invention is to provide a method for phosphating objects with cavities, which have been obtained by joining steel sheets and galvanized steel sheets or by partial galvanizing of steel sheets (composite metals), which does not have the disadvantages of the aforementioned methods, but - without additional procedural effort - leads to a perfect closed phosphate layer.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß die Gegenstände zur Einleitung der Phosphatschichtausbildung maximal 30 s in eine Phosphatierungslösung auf Basis Zinkphosphat vorgetaucht und dann der Zone der eigentlichen Tauchphosphatierung zugeführt werden.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 objects for initiating the formation of the phosphate layer are pre-immersed in a phosphating solution based on zinc phosphate for a maximum of 30 s and then fed to the zone of the actual immersion phosphating.
Zwar ist es aus der JP - A - 81 119 780 bekannt, kaltgewalzte oder verzinkte Stahlbleche vor der üblichen Phosphatierung mit der gleichen Art von Phosphatierungslösung vorzubehandeln. Hierbei handelt es sich jedoch nicht um ein Verfahren zum Phosphatieren von Verbundmetallen, d.h. von Gegenständen, die sowohl freie Stahl- als auch freie Zinkoberflächen aufweisen.It is known from JP-A-81 119 780 to pretreat cold-rolled or galvanized steel sheets with the same type of phosphating solution before the usual phosphating. However, this is not a process for phosphating composite metals, i.e. of objects that have both free steel and free zinc surfaces.
Zur Durchführung der Phosphatierung sind beliebige Phosphatierungslösungen auf Basis Zinkphosphat einsetzbar. Sie können sowohl der sogenannen Niedrigzink- als auch der Normalzink-Technologie angehören. D.h. die Verbundmetalle können mit einer Phosphatierungslösung, in der das Gewichtsverhältnis von Zn zu P205 auf 1 : (8 bis 85) eingestellt ist, oder aber mit einer Phosphatierungslösung, in der das Gewichtsverhältnis von Zn zu P205 auf 1 : (0,3 bis 7) eingestellt ist, in Berührung gebracht werden.Any phosphating solutions based on zinc phosphate can be used to carry out the phosphating. You can belong to the so-called low zinc as well as the normal zinc technology. That is, the composite metals can with a phosphating solution in which the weight ratio of Zn to P 2 0 5 is set to 1: (8 to 85), or with a phosphating solution in which the weight ratio of Zn to P 2 0 5 to 1: (0.3 to 7) is set.
Im ersten Fall entstehen auf Stahl Phosphatschichten mit einem hohen Anteil an Phosphophyllit zu Hopeit. Diese Überzüge eignen sich wegen ihres ausgezeichneten Korrosionsschutzes insbesondere als Vorbereitung für die Lakkierung, wobei die besten Schutzeigenschaften in Verbindung mit der kathodischen Elektrotauchlackierung erzielt werden.In the first case, 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 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 and a certain amount of free acid which is matched to the respective bath concentration, type of application and bath temperature. Depending on the process conditions, the pH of the baths is approximately between 2.0. and 3.9.
Die Bäder können ferner in der Phosphatiertechnik bekannte weitere Kationen, z. B. Ni, Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH4 u.a., enthalten. Zur Einstellung des Säureverhältnisses und zur Erzielung spezieller technischer Effekte kann die Mitverwendung weiterer, von Phosphat verschiedener Anionen, z. B. N03, C103, Cl, S04, F, BF4, SiF6, Citrat, Tartrat u.a., erforderlich bzw. wünschenswert sein.The baths can also known in the phosphating technology other cations, for. B. Ni, Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH4, etc. included. To adjust the acid ratio and to achieve special technical effects, the use of other, different from phosphate anions, z. B. N0 3 , C10 3 , Cl, S0 4 , F, BF 4 , SiF 6 , citrate, tartrate, etc., may be necessary or desirable.
Die Kontaktzeit für die in der abschließenden Tauchbehandlung zum Einsatz kommenden Phosphatierungslösung liegt üblicherweise zwischen 1 und 10 min. 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 final immersion treatment is usually between 1 and 10 minutes. The temperature of the phosphating solution is approximately 30 to 60 ° C. The lower the temperature, the longer the contact time.
Eine vorteilhafte Ausführungsform der Erfindung besteht darin, die Gegenstände (Verbundmetalle) während der Zuführung zur Zone der Tauchphosphatierung mit Phosphatierungslösung auf Basis Zinkphosphat zu bespritzen und weiterhin die Zuführung zur Zone der Tauchphosphatierung und damit die Spritzbehandlung auf maximal 30 s einzustellen.An advantageous embodiment of the invention consists of spraying the objects (composite metals) with phosphating solution based on zinc phosphate during the feed to the immersion phosphating zone, and further adjusting the supply to the immersion phosphating zone and thus the spray treatment to a maximum of 30 s.
Diese Arbeitsweise hat den Vorzug, daß während der Übergabe der Metalloberfläche in die abschließende Tauchbehandlung frische Phosphatierungslösung zur Ausbildung eines gleichbleibenden Flüssigkeitsfilms auf der Metall- oberfläche zur Verfügung steht. Es wird also vermieden, daß durch Ablaufen der Flüssigkeit unterschiedlich dicke Flüssigkeitsfilme auf der Metalloberfläche vorhanden sind. Der Vorteil der vorgenannten Maßnahme zeigt sich insbesondere in der Ausbildung gleichmäßiger Phosphatschichten.This procedure has the advantage that fresh phosphating solution is available during the transfer of the metal surface into the final immersion treatment in order to form a constant liquid film on the metal surface. It is thus avoided that liquid films of different thicknesses are present on the metal surface as the liquid runs off. The advantage of the aforementioned measure is particularly evident in the formation of uniform phosphate layers.
Im übrigen sind auch beim vorliegenden Verfahren die im Zushmmenhang 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.For the rest, 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.
Wenn in den vorstehenden Ausführungen im Zusammenhang mit der eigentlichen Tauchbehandlung, dem kurzzeitigen Tauchen vor der Übergabe und der Spritzbehandlung während der Zuführung der Verbundmetallen zur Tauchbehandlung von Phosphatierungslösungen auf Basis Zinkphosphat gesprochen wird, so handelt es sich hierbei üblicherweise um Lösungen von im wesentlichen gleicher Zusammensetzung. Gewisse Abweichungen sind in der Regel vorwiegend die Folge unterschiedlicher Abarbeitung der Phosphatierungslösung und der verstärkten Eisenfällung durch Einwirkung von Luftsauerstoff bei der Spritzbehandlung.If in the above statements in connection with the actual immersion treatment, the brief immersion before delivery and the spray treatment during the supply of the composite metals for immersion treatment of phosphating solutions based on zinc phosphate, these are usually solutions of essentially the same composition. Certain deviations are usually primarily the result of different processing of the phosphating solution and the increased iron precipitation due to the action of atmospheric oxygen during the spray treatment.
Die Erfindung wird anhand der Beispiele beispielsweise und näher erläutert.The invention is illustrated by way of example and in more detail.
Verbundmetalle aus Stahlblech und verzinktem Stahlblech wurden nach folgenden Arbeitsgängen behandelt.
- 1) Vorreinigung mit einem alkalischen Reiniger bei 60° C während 4 min. Spritzen.
- 2) Hauptreinigung mit dem gleichen Reiniger bei 80° C; während 9,5 min. Tauchen.
- 3) Spülung mit Kaltwasser im Tauchen.
- 4) Aktivierung mit einer Titanphosphatlösung während 1 min. im Tauchen.
- 5) Phosphatierung bei 60° C mit einer Lösung, die
- 1,5 g/I Zn
- 0,4 g/I Ni
- 22,5 g/l P205
- 0,14 g/I HaN02
- enthält und
- freie Säure 1,6 bis 1,7 Punkte
- Gesamtsäure 36 Punkte sowie
- einen s-Wert von 0,05 bis 0,06
- aufweist.
- 6) Spülung mit Kaltwasser im Tauchen.
- 7) Nachspülung mit einer Crlll/CrVI-Lösung im Tauchen.
- 8) Trocknung im Ofen während 15 min.
- 1) Pre-cleaning with an alkaline cleaner at 60 ° C for 4 min. Syringes.
- 2) Main cleaning with the same cleaner at 80 ° C; during 9.5 min. Diving.
- 3) Rinsing with cold water while diving.
- 4) Activation with a titanium phosphate solution for 1 min. in diving.
- 5) Phosphating at 60 ° C with a solution that
- 1.5 g / l Zn
- 0.4 g / l Ni
- 22.5 g / l P 2 0 5
- 0.14 g / l HaN0 2
- contains and
- free acid 1.6 to 1.7 points
- Total acidity 36 points as well
- an s value of 0.05 to 0.06
- having.
- 6) Rinsing with cold water while diving.
- 7) Rinse with a Crlll / CrVI solution while diving.
- 8) drying in the oven for 15 min.
Bei gleichen Bedingungen hinsichtlich der Stufen 1 bis 4 und 6 bis 8 wurden innerhalb der Phorphatierstufe Tauchund Spritzzeiten entsprechend der Eintragung in der nachfolgenden Tabelle variiert.
Die Versuche zeigen, daß bei alleiniger Tauchphosphatierung (1) am Rand zur Zinkoberfläche ein Streifen mit nur unvollständig ausgebildeter und daher durchscheinender Phosphatschicht erhalten wird. Bei einer davor geschalteten Spritzbehandlung (2 bis 4) ist dieser Streifen zwar einwandfrei phosphatiert und trägt eine geschlossene Phosphatschicht, jedoch ist die gesamte Stahloberfläche mit streifigen Phosphatschichten bedeckt.The experiments show that with immersion phosphating alone (1), a strip with an incompletely formed and therefore translucent phosphate layer is obtained at the edge of the zinc surface. In the case of a spray treatment (2 to 4) connected upstream, this strip is perfectly phosphated and has a closed phosphate layer, but the entire steel surface is covered with streaked phosphate layers.
Bei einem zusätzlichen Vortauchen entsprechend dem Verfahren gemäß Erfindung (5 bis 7) ist die Phosphatschichtausbildung sowohl in der Nähe der Zinkoberfläche als auch auf der gesamten Stahloberfläche einwandfrei.In the case of an additional preliminary dipping according to the method according to the invention (5 to 7), the phosphate layer formation is flawless both in the vicinity of the zinc surface and on the entire steel surface.
Bei längerem Vortauchen bleibt zwar die Phosphatschicht auf der Stahloberfläche geschlossen, im Wirkungsbereich der Zinkoberfläche ist sie jedoch unvollständig ausgebildet und durchscheinend.The phosphate layer on the steel surface remains closed after prolonged diving, but it is incomplete and translucent in the area of action of the zinc surface.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3315086 | 1983-04-26 | ||
| DE19833315086 DE3315086A1 (en) | 1983-04-26 | 1983-04-26 | METHOD FOR PHOSPHATING COMPOSITE METALS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0127204A1 EP0127204A1 (en) | 1984-12-05 |
| EP0127204B1 true EP0127204B1 (en) | 1988-01-13 |
Family
ID=6197396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84200398A Expired EP0127204B1 (en) | 1983-04-26 | 1984-03-20 | Phosphating process for composite metals |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4559087A (en) |
| EP (1) | EP0127204B1 (en) |
| JP (1) | JPS59205482A (en) |
| AU (1) | AU566551B2 (en) |
| BR (1) | BR8401938A (en) |
| CA (1) | CA1225310A (en) |
| DE (2) | DE3315086A1 (en) |
| ES (1) | ES8501450A1 (en) |
| GB (1) | GB2138844B (en) |
| NZ (1) | NZ207947A (en) |
| PT (1) | PT78409B (en) |
| ZA (1) | ZA843104B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
| EP0653502A3 (en) * | 1993-11-11 | 1995-08-09 | Nihon Parkerizing | Composite article of steel plated with a metal containing zinc and production process. |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE452007A (en) * | 1942-05-05 | |||
| US2552874A (en) * | 1950-05-01 | 1951-05-15 | American Chem Paint Co | Method of phosphatizing ferriferous surfaces |
| BE635605A (en) * | 1962-08-01 | |||
| GB1084017A (en) * | 1963-09-30 | 1967-09-20 | Jawata Iron & Steel Co Ltd | Pretreating process for phosphate-treating steel sheets or plated steel sheets |
| JPS4824135B1 (en) * | 1968-12-20 | 1973-07-19 | ||
| ZA722987B (en) * | 1971-05-10 | 1973-02-28 | Craig S Investments Pty Ltd | Rust proofing process |
| DE2207047A1 (en) * | 1972-02-15 | 1973-08-30 | Metallgesellschaft Ag | PROCESS FOR THE PREPARATION OF STEEL PIECES FOR CHIPLESS COLD FORMING |
| SE406940B (en) * | 1974-04-13 | 1979-03-05 | Collardin Gmbh Gerhard | PROCEDURE FOR PREPARING PHOSPHATE COATINGS BY THE IRON AND STEEL SPRAYING METHOD |
| JPS5811513B2 (en) * | 1979-02-13 | 1983-03-03 | 日本ペイント株式会社 | How to protect metal surfaces |
| JPS57152472A (en) * | 1981-03-16 | 1982-09-20 | Nippon Paint Co Ltd | Phosphating method for metallic surface for cation type electrodeposition painting |
| US4400416A (en) * | 1981-05-19 | 1983-08-23 | Toyota Jidosha Kogyo Kabushiki Kaisha | Method of surface treatment and an apparatus used in said surface treatment |
-
1983
- 1983-04-26 DE DE19833315086 patent/DE3315086A1/en not_active Withdrawn
-
1984
- 1984-03-20 DE DE8484200398T patent/DE3468702D1/en not_active Expired
- 1984-03-20 EP EP84200398A patent/EP0127204B1/en not_active Expired
- 1984-03-30 ES ES531203A patent/ES8501450A1/en not_active Expired
- 1984-04-11 PT PT78409A patent/PT78409B/en not_active IP Right Cessation
- 1984-04-17 US US06/600,587 patent/US4559087A/en not_active Expired - Fee Related
- 1984-04-24 CA CA000452666A patent/CA1225310A/en not_active Expired
- 1984-04-25 JP JP59083586A patent/JPS59205482A/en active Pending
- 1984-04-25 BR BR8401938A patent/BR8401938A/en unknown
- 1984-04-26 ZA ZA843104A patent/ZA843104B/en unknown
- 1984-04-26 NZ NZ207947A patent/NZ207947A/en unknown
- 1984-04-26 AU AU27280/84A patent/AU566551B2/en not_active Ceased
- 1984-04-26 GB GB08410726A patent/GB2138844B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4559087A (en) | 1985-12-17 |
| DE3468702D1 (en) | 1988-02-18 |
| BR8401938A (en) | 1984-12-04 |
| DE3315086A1 (en) | 1984-10-31 |
| AU2728084A (en) | 1984-11-01 |
| CA1225310A (en) | 1987-08-11 |
| AU566551B2 (en) | 1987-10-22 |
| ES531203A0 (en) | 1984-12-01 |
| GB2138844B (en) | 1986-06-18 |
| NZ207947A (en) | 1987-09-30 |
| PT78409A (en) | 1984-05-01 |
| EP0127204A1 (en) | 1984-12-05 |
| ZA843104B (en) | 1984-11-28 |
| PT78409B (en) | 1986-05-27 |
| ES8501450A1 (en) | 1984-12-01 |
| JPS59205482A (en) | 1984-11-21 |
| GB2138844A (en) | 1984-10-31 |
| GB8410726D0 (en) | 1984-05-31 |
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